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chemical bonding

chemistry
Main
any of the interactions that account for the association of atoms into molecules, ions,
crystals, and other stable species that make up the familiar substances of the everyday
world. When atoms approach one another, their nuclei and electrons interact and tend to
distribute themselves in space in such a way that the total energy is lower than it would
be in any alternative arrangement. If the total energy of a group of atoms is lower than the
sum of the energies of the component atoms, they then bond together and the energy
lowering is the bonding energy.
The ideas that helped to establish the nature of chemical bonding came to fruition during
the early 20th century after the electron had been discovered and quantum mechanics had
provided a language for the description of the behaviour of electrons in atoms. owever,
even though chemists need quantum mechanics to attain a detailed quantitative
understanding of bond formation, much of their pragmatic understanding of bonds is
e!pressed in simple, intuitive models. These models treat bonds as primarily of two kinds
"namely, ionic and covalent. The type of bond that is most likely to occur between two
atoms can be predicted on the basis of the location of the elements in the periodic table,
and to some e!tent the properties of the substances so formed can be related to the type of
bonding.
# key concept in a discussion of chemical bonding is that of the molecule. $olecules are
the smallest units of compounds that can e!ist. %ne feature of molecules that can be
predicted with reasonable success is their shape. $olecular shapes are of considerable
importance for understanding the reactions that compounds can undergo, and so the link
between chemical bonding and chemical reactivity is discussed briefly in this article.
#lthough simple models of bonding are useful as rules of thumb for rationali&ing the
e!istence of compounds and the physical and chemical properties and structures of
molecules, they need to be 'ustified by appealing to more sophisticated descriptions of
bonding. $oreover, there are some aspects of molecular structure that are beyond the
scope of the simple theories. To achieve this insight, it is necessary to resort to a fully
quantum mechanical description. In practice, these descriptions entail heavy reliance on
computers. (uch numerical approaches to the chemical bond provide important
information about bonding.
This article begins by describing the historical evolution of the current understanding of
chemical bonding and then discusses how modern theories of the formation of chemical
bonds have emerged and developed into a powerful description of the structure of matter.
#fter the historical introduction, qualitative models of bonding are discussed, with
particular attention given to the formation of ionic and covalent bonds and the correlation
of the latter with molecular shapes. The more sophisticated quantum mechanical
approaches to bond formation are then described, followed by a survey of a number of
special cases that raise interesting problems or lead to important insights.
)or a detailed discussion of the structure and properties of atoms, see the article atom.
*hemical compounds are surveyed in the article chemical compound, and the elements
are described in the article chemical element.
Historical review Emergence of quantitative chemistry
The early +reeks, most notably ,emocritus, argued that matter is composed of
fundamental particles called atoms. The views of the atomists, however, lacked the
authority that comes from e!periment, and evidence of the e!istence of atoms was not
forthcoming for two millennia until the emergence of quantitative, empirical science in
the -.th century.
Historical review Emergence of quantitative chemistry The law of
conservation of mass
The crucial transformation of chemistry from a collection of vain hopes and alchemical
meddlings to a corpus of reliable quantitative knowledge hinged on the contributions of
the )rench aristocrat #ntoine/0aurent 0avoisier 1and his wife, $arie/#nne2, shortly
before he lost his head to the guillotine at the height of the 3eign of Terror. 0avoisier
opened the door to quantitative chemistry by establishing that the transformations of
matter, which until his day had been described largely by a miasma of uncoordinated
reports, could be investigated quantitatively by measuring the masses of substances
consumed and produced in reactions. The most significant observation he made was that,
even though one substance is transformed into another during the course of a reaction, the
total mass of the products is the same as the total mass of the reactants. The implication
of this observation is that, although the identity of the substances may change when a
reaction occurs, something, at least, remains unchanged.
Historical review Emergence of quantitative chemistry The law of constant
composition
0avoisier4s e!perimentation inspired further studies that ultimately resulted in an
overthrow of the view that matter is a structureless continuum. These observations
culminated in the atomic hypothesis developed by the 5nglish chemist 6ohn ,alton,
which states that matter is composed of indestructible particles which are unique to and
characteristic of each element. Two ma'or sets of observations helped to establish this
view. )irst, it was found that compounds always have a fi!ed composition, regardless of
their origin. Thus, it was determined that -. grams of water always consists of 2 grams of
hydrogen and -7 grams of o!ygen, regardless of how the sample originated. (uch
observations overthrew, at least temporarily, the view held by the )rench chemist *laude/
0ouis 8erthollet that compounds have a variable composition. $odern research has
shown, however, that there are in fact certain classes of compound in which the
composition is variable. 9evertheless, they are a minority, and the law of constant
composition is the rule rather than the e!ception.
Historical review Emergence of quantitative chemistry The law of multiple
proportions
The second step toward ,alton4s synthesis was the recognition of the e!istence of related
series of compounds formed by the same elements. It was established, for e!ample, that,
whereas 2. grams of carbon mono!ide invariably consists of -2 grams of carbon and -7
grams of o!ygen, carbon also forms the compound carbon dio!ide, and :: grams of this
compound always consists of -2 grams of carbon and ;2 grams of o!ygen. In this
e!ample, the mass of o!ygen that combines with a fi!ed mass of carbon to form carbon
dio!ide is e!actly twice the quantity that combines to form carbon mono!ide. (uch
observations strongly suggested that carbon dio!ide contains e!actly twice as many
o!ygen entities per carbon entity as carbon mono!ide does. ,alton predicted that, when
two elements combine in a series of compounds, the ratios of the masses of one element
that combine with a fi!ed mass of the second are reducible to small whole numbers< this
is now known as the law of multiple proportions.
Historical review Emergence of quantitative chemistry Daltons atomic
theory
,alton brought these observations together and thereby established a language that, with
minor emendation, has become universal in chemistry. e proposed that elements are
composed of indestructible atoms, that each atom of an element is identical, that atoms of
different elements differ in terms of mass, and that compounds consist of characteristic
groupings of atoms. 8ecause a compound is characteri&ed by the grouping of atoms and
each atom has a characteristic mass, it was at once easy to understand that compounds
have a fi!ed composition by mass. $oreover, the e!istence of related families of
compounds, which differ in an integral manner in their composition by mass, could
immediately be e!plained by supposing that the various compounds differ in the number
of atoms of one element that combine with one atom of a second element. *arbon
mono!ide, for instance, consists of one atom of carbon linked to one atom of o!ygen,
whereas carbon dio!ide consists of one atom of carbon linked to two atoms of o!ygen.
Thus, in modern terms, carbon mono!ide is denoted *%, whereas carbon dio!ide is
denoted *%2.
Historical review Features of bonding Valence
The chemists of the -=th century established a large body of empirical information
leading to the reali&ation that patterns e!ist in the types of compounds that elements can
form. The most useful rationali&ing characteristic of an element is its valence, which was
originally defined in terms of the ma!imum number of hydrogen atoms that could attach
to an atom of the element. ydrogen was selected as the probe of valence because
investigators discovered that an atom of hydrogen is never found in combination with
more than one other atom and thus regarded it as the most primitive of the elements. In
this way it was established that o!ygen 1%2 typically has a valence of 2 1as in water,
2%2, nitrogen 192 a valence of ; 1as in ammonia, 9;2, and chlorine 1*l2 a valence of -
1as in hydrogen chloride, *l2. 5!amining the patterns of bonding between elements
made it possible to ascribe typical valences to all elements even though their compounds
with hydrogen itself were unknown.
#lthough the concept of valence was highly suggestive of an intrinsic property of atoms,
there were some pu&&ling aspects, such as the observation that some elements appear to
have more than one common valence. The element carbon, for e!ample, is found to have
typical valences of 2 and :.
Historical review Features of bonding onic and covalent compounds
# second general feature of bonding also became apparent in the early days of chemistry.
It was found that there are two large classes of compound that can be distinguished by
their behaviour when dissolved in water. %ne class consists of electrolytes> these
compounds are so called because they dissolve to give solutions that conduct electricity.
$embers of the other class, nonelectrolytes, dissolve to yield solutions that do not
conduct electricity. The difference between the two classes gave rise to the view that
there are two types of chemical bond. 5lectrolytes produce ions in solution< an ion is an
electrically charged atom and transports its electric charge as it moves through a solution.
5lectrolytes therefore either consist of ions before they are dissolved or produce ions
upon dissolving. 9onelectrolytes do not produce ions when they dissolve and do not
consist of ions in their undissolved state.
It became apparent that some compounds are composed of ions, whereas others are
composed of groups of atoms that are held together in a different manner. The latter
compounds are termed covalent. In fact, it took a long time for the view to be confirmed
that ions e!ist even before dissolution occurs, and only in the early 20th century was
crucial evidence obtained that showed the presence of distinct entities, specifically
sodium cations 1positively charged atoms2, 9a
?
, and chloride anions 1negatively charged
atoms2, *l
@
, in solid sodium chloride 19a*l2.
Historical review The periodic table
The pattern of valence and the type of bonding"ionic or covalent"characteristic of the
elements were crucial components of the evidence used by the 3ussian chemist ,mitry
Ivanovich $endeleyev to compile the periodic table, in which the chemical elements are
arranged in a manner that shows family resemblances. Thus, o!ygen and sulfur 1(2, both
of which have a typical valence of 2, were put into the same family, and nitrogen and
phosphorus 1A2, with a typical valence of ;, were put into a neighbouring family. The
periodic table, which is shown in )igure - , has proved to be the single
most unifying concept of chemistry, for it summari&es a wealth of properties. $etallic
elements generally lie to the left in the table and typically form ionic compounds.
9onmetallic elements, which form a large number of covalent compounds among
themselves, typically lie to the right in the table. If for now the special case of the band of
elements of columns ; through -2 of the table, called the transition elements, is ignored,
then the typical valences of elements increase from - on the far left, rising in steps of -
on passing to the right, to reach : at the family headed by carbon 1*2 and then fall in
steps of - to - itself at the family that contains chlorine and is headed by fluorine 1)2.
ere, at last, is a pattern of valence that any e!planation of chemical bond formation
needs to 'ustify.
Bnknown to $endeleyev, and not discovered until the late -=th century and the
beginning of the 20th, is another family of elements that were originally thought to be
inert and hence were called the inert gases. This family is headed by helium 1e2 and
includes neon 19e2, argon 1#r2, krypton 1Cr2, !enon 1De2, and radon 13n2. It was not
until the -=70s that their chemical inertness was overcome, and some members of the
family 1essentially only krypton and !enon2 were induced to form compounds.
#ccordingly, the name inert gas was replaced by the term noble gas, which reflects a
chemical aloofness but not total inertness. This family of elements might at first have
seemed irrelevant to an understanding of chemical bonds. owever, the very fact that
they do not readily form any bonds proved to be crucial to the development of modern
theories of bond formation.
Historical review !dditional evidence of atoms !vogadros law
Bntil the early 20th century some regarded the atomic hypothesis as no more than an
unsubstantiated hypothesis or a convenient accounting device. The reality of atoms and
the molecules they formed was widely advocated but by no means universally accepted<
however, opposition to the reality of atoms diminished as e!perimental evidence
accumulated. #mong such historically significant evidence were the quantitative
measurements of the volumes of gases. Thus, it was noted that, when water is
decomposed by electrolysis 1i.e., by passing an electric current through it2, the gases
hydrogen and o!ygen are produced in the ratio of 2>- by volume. This observation led the
Italian scientist #medeo #vogadro to propose that equal volumes of gases 1at the same
temperature and pressure2 contain equal numbers of molecules. The electrolysis of water
was then seen to be consistent with a water molecule formed of two hydrogen atoms and
one o!ygen atom and hence consistent with the chemical formula 2%. 1It is now known
that hydrogen gas consists of 2 molecules and o!ygen gas of %2 molecules, but this
important detail does not upset the interpretation.2
Historical review !dditional evidence of atoms "inetic theory of gases
The measured volumes of gases supported the claims of the e!istence of atoms and
molecules. The emergence of the science of mechanics furthered the understanding of
atoms and molecules, as the properties of gases were predicted based on the assumption
that they are composed of minute particles in ceaseless chaotic motion. )rom this kinetic
model of gases 1see gas> Cinetic theory of gases2, it was possible to calculate the pressure
e!erted by a gas and the average speed of its molecules, and e!cellent agreement with
observation was obtained.
Historical review !dditional evidence of atoms Visual images of atoms
The last opposition to the e!istence of atoms vanished in the early 20th century when
techniques were developed that portrayed visual representations of atoms. The first such
techniques made use of the diffraction of D rays, where the pattern of interference
between rays that are reflected by a crystal can be interpreted in terms of the scattering
from individual atoms. $ore images of atoms were produced in the -=70s by using
methods that stripped electrons out of arrays of atoms at the surfaces of solids so that a
map of the surface could be made, as well as by using improved techniques in electron
microscopy that increased the resolving power of the microscope to nearly the point
where individual atoms could be distinguished. The most recent and visually compelling
evidence came in the -=.0s with the development of scanning tunneling microscopy. In
this technique a needle point sharpened to consist of a single atom is moved like a
delicate plow 'ust above the surface of a sample, and its position is monitored. The results
appear in the form of a visual image of the sample4s surface. The technique has been
perfected to a point where it can be used to determine the locations of individual atoms.
%f these techniques, electron microscopy comes the closest to an actual EsightingF of an
atom, as the image requires the least construction. Images are obtained from D/ray
diffraction data only after intense mathematical manipulation. 8oth field/emission and
scanning tunneling microscopy give portrayals of the properties of a surface on an atomic
scale and show atomlike features.
Historical review Molecular structure
$ost chemists were confident that atoms really e!ist long before these sophisticated
techniques provided such irrefutable evidence. In the -=th century, when the
compositions of countless compounds were being determined, it was found that in certain
cases different compounds have the same chemical composition. Thus, the composition
*;: was found for two entirely different organic compounds 1as 'udged by both their
physical and chemical properties2"namely, propyne and allene. *onfident about their
analyses, chemists were forced to the conclusion that the two compounds differ in the
manner in which their constituent atoms are linked together. In modern terms, the
compounds are represented, respectively, as>

1The nature of the links between atoms is the ma'or topic of this article and is discussed
in detail below.2 Thus, the sense of molecular structure 1i.e., the arrangement of atoms in
space2 entered chemistry and, by implication, supported the view that atoms are real.
#bout the same time 1in the -.70s2, a more subtle aspect of structure became apparent"
that of the three/dimensional spatial disposition of atoms in molecules. The concept of
molecular structure began with the reali&ation that atoms have different neighbours in
different compounds even though their overall chemical compositions might be the same
1as in the two structures corresponding to the formula *;:2. This is a topological
distinction, meaning that the distinction is based on which atom is linked to which atom.
The additional distinction introduced is geometric, referring to the spatial disposition of
atoms relative to one another. #s an e!ample of this kind of distinction, the compound
dichloromethane 1*2*l22 can be considered. The topological structure of this molecule
is>
with the hydrogen and chlorine atoms linked to a central carbon atom. It was observed
that there is only one such compound. The significance of this is that the molecule cannot
be planar, because, if that were the case, two different molecules of formula *2*l2
would be found>
The fact that there is only one dichloromethane suggests that its molecules are
tetrahedral, for then, in whichever arrangement the four hydrogen and chlorine atoms are
linked to the central carbon atom, the molecule is identical 1apart from its orientation in
space, which is irrelevant2>
With observations such as this, the sense of molecular shape entered chemistry and since
then has assumed a central and fundamental position.
9ineteenth/century chemists had to infer the shapes of molecules from clever but indirect
e!perimentation. The modern understanding of molecular shape is more direct 1if one
discounts the computing that intervenes between observation and representation2. In
particular, D/ray diffraction has provided incomparably detailed images of molecules
even as large as those of proteins, which contain thousands of atoms. (canning tunneling
microscopy, although much more recent in inception, has provided realistic images that
confirm beyond doubt the essential features of molecular geometry.
The importance of the determination 1and understanding2 of molecular structure cannot
be overestimated. #t the simplest level, the properties of small molecules 1including the
ubiquitous and important water molecule, 2%2 stem in large measure from their shapes
and not merely from their atomic compositions. The oceans, for instance, might not e!ist
if water molecules were linear rather than angular, for the interactions between 2%
molecules would not be as strong, and hence it is doubtful whether life would have
emerged if water molecules were linear. #t the most comple! level, that of proteins,
geometric structure is essential to biochemical function and thus has a critical role in all
living systems.
Historical review Internal structure of atoms
The concept of atoms thus emerged from the meticulous measurement of mass and
volume, which in the earliest days of chemistry were the only quantitative probes of
matter available. The reality of atoms was established by the e!planatory power of the
model on the one hand and by ever more direct images of microscopic entities on the
other. #s the atomic model of matter became more firmly established, attention turned to
the e!istence of molecules, which are specific assemblages of atoms. #s molecules were
e!amined, it was discovered that they have characteristic links between atoms and that
the atoms are positioned in three/dimensional arrangements that are characteristic of the
compound and of the constituent atoms.
Historical review nternal structure of atoms Discovery of the electron
The questions raised by this fund of knowledge remained unanswered until the internal
structure of atoms began to be unraveled at the end of the -=th century. The classic view,
proposed by ,alton, that atoms are irreducible, unchangeable entities virtually eliminated
the prospect of understanding their properties, for it implied the absence of internal
structure. The mutability of atoms, and hence the first glimmerings of an understanding
of their constitution and their properties, came with the discovery of the electron as a
universal constituent of matter. The electron was the first subatomic particle to be
discovered and in due course proved to be the most important one for the e!planation of
the chemical bond. This importance stems in large part from the ease with which
electrons can be removed from one atom and transferred to another. #s will be seen
below, this transferability of electrons is the key to bond formation, and all theories of the
chemical bond focus on the redistribution of an atom4s electrons when it links to another
atom.
$ore will be said about the essential features of the arrangement of electrons in atoms in
the following section. The key to understanding the structure of the periodic table and
hence the pattern of bonding between atoms was the reali&ation that electrons are
arranged in shells that surround a central positively charged nucleus. 5ach shell can
contain a characteristic ma!imum number of electrons. The outermost shell contains the
electrons that are involved in bond formation, for they are the least tightly bound to the
nucleus and thus can be removed most readily. This shell is called the valence shell. The
most important feature of the valence shell is that for the noble gases it is complete 1in
the sense e!plained below2 with its full complement of electrons 1i.e., eight, e!cepting the
case of helium2. Thus, the formation of chemical bonds appears to be related to the
incompleteness of the valence shell.
Historical review nternal structure of atoms #ontributions of $ewis
The role of the valence shell in bond formation was e!pounded by the #merican chemist
+ilbert 9. 0ewis about -=-7. Important independent studies were made by Walther
Cossel, and later contributions followed from Irving 0angmuir. )irst, 0ewis proposed
that ionic bonds are formed by the complete transfer of electrons from the valence shell
of one atom into the valence shell of another atom and that the transfer proceeds until the
valence shells of both have reached the electronic composition characteristic of the
nearest noble gas atom in the periodic table. Thus, sodium has one electron in its valence
shell, and its loss results in a singly charged cation, 9a
?
, with a neonlike arrangement of
electrons. *hlorine, on the other hand, has a valence shell that needs one more electron to
achieve the closed shell characteristic of its noble gas neighbour, argon, and so readily
forms the singly charged anion *l
@
. Thus, it is easy to comprehend the formation of
sodium chloride as a collection of 9a
?
ions and *l
@
ions.
0ewis proposed that a covalent bond consists of two electrons that are shared between
atoms rather than being fully donated by one atom to another. e had no means of
knowing why a pair of electrons should be so important 1that understanding would come
only later with the introduction of quantum mechanics2, but his insight rationali&ed a
great body of chemical facts. #s in the formation of ionic bonds, 0ewis emphasi&ed the
importance of the nearest/noble/gas valence shell and proposed that, as in the formation
of ionic bonds, electron sharing continues until each atom possesses a noble gas
configuration.
In summary, 0ewis4 ideas are e!pressed by his celebrated octet rule, which states that
electron transfer or electron sharing proceeds until an atom has acquired an octet of
electrons 1i.e., the eight electrons characteristic of the valence shell of a noble gas atom2.
When complete transfer occurs, the bonding is ionic. When electrons are merely shared,
the bonding is covalent, and each shared electron pair constitutes one chemical bond.
(uch is the basis of the theory of chemical bonding that is still widely held. There is
much to e!plain and more to understand, however, and there are many important
e!ceptions to 0ewis4 ideas, which cannot as a consequence provide a complete
e!planation of bonding. The following sections step back from this historical account and
put 0ewis4 important ideas in a broader conte!t that will show more of their power. #t the
same time the more advanced treatment of bonding will transcend 0ewis4 ideas and
account for features of bonding that his views could not embrace.
Atomic structure and bonding
To understand bond formation, it is necessary to know the general features of the
electronic structure of atoms"that is, the arrangement of electrons around the central
nucleus. )or background information about this sub'ect and further details, see the article
atom.
Atomic structure and bonding Atomic structure
The modern version of atomic structure begins with 5rnest 1later 0ord2 3utherford4s
recognition that an atom consists of a single, central, massive, positively charged nucleus
surrounded by electrons. The number of protons in the nucleus is the atomic number, Z,
of the element. 1)or hydrogen Z G -, and for carbon Z G 7.2 # proton is positively
charged, and an electron carries an equal but opposite negative charge. )or an atom to be
electrically neutral, it must contain the same number of e!tranuclear electrons as there are
protons in the nucleus. ence, the number of electrons in a neutral atom of atomic
number Z is also Z. # hydrogen atom consequently has one electron, and a carbon atom
has si! electrons.
!tomic structure and bonding !tomic structure The %ohr model
The first attempt to introduce quantum theory to account for the structure of atoms was
made by the ,anish physicist 9iels 8ohr in -=-;. e asserted that the electron in a
hydrogen atom occupies one of an array of discrete 1but infinite in number2 orbits, each
orbit being progressively farther from the nucleus and labeled with an integer n G -,
2, . . . . This integer is an e!ample of a quantum number, which in general is an integer
1in some cases, a half/integer2 that labels the state of a system and which, through an
appropriate formula, determines the values of certain physical properties of the system.
8y matching the centrifugal effect of the electron4s motion in its orbit to the electrostatic
attraction of the nucleus for the electron, 8ohr was able to find a relation between the
energy of the electron and the quantum number of its orbit. The result he obtained was in
almost perfect agreement with the observed values of the energy levels of a hydrogen
atom that had previously been obtained by spectroscopic methods.
8ohr4s triumph was the first apparently successful incorporation of quantum theoretical
ideas into the description of a mechanical system. The numerical success of the model
has turned out to be coincidental, however, and 8ohr4s model is now regarded as no more
than a historically important step in the evolution of quantum mechanics. The cracks in
its validity were noted quite soon after its introduction. Thus, it was remarked that 8ohr
had not really derived the e!istence of discrete orbits from more fundamental principles
but had merely imposed them on the model. )urthermore, all attempts to e!tend his
theory to atoms that consisted of more than one electron 1helium, with two electrons, for
instance2 utterly failed. #lthough the model was augmented by more elaborate
specifications of the orbits 1most notably, first, by allowing for elliptical orbits and
introducing a second quantum number to specify the elongation of the ellipse and,
second, by allowing for the effects of relativity2, the failure to generali&e to many/
electron atoms remained a fatal flaw.
!tomic structure and bonding !tomic structure The quantum mechanical
model
*urrent understanding of atomic structure had to await the introduction of quantum
mechanics by the scientists Werner eisenberg of +ermany and 5rwin (chrHdinger of
#ustria in the mid/-=20s. Indeed, the structure of the hydrogen atom that is still
employed today was developed by (chrHdinger in the four papers with which he
introduced his version of quantum mechanics"wave mechanics"to the world. The
quantum mechanical model of the hydrogen atom has the same numerical agreement with
e!periment that proved so coincidental with the 8ohr model, but it is more fundamentally
founded 1i.e., the discreteness of the allowed energy states emerges from more general
aspects and is not imposed2, and the model can be e!tended 1albeit with difficulty2 to
many/electron atoms. $oreover, unlike 8ohr4s theory, it is consistent with the
fundamental principles of quantum mechanics"specifically the wave character of the
electron and the requirements of the uncertainty principle, which states that the position
and momentum 1mass times velocity2 of a particle cannot be specified simultaneously.
Atomic structure and bonding Atomic structure The quantum mechanical model The
location of the electron
In the quantum mechanical model of the hydrogen atom, the location of the electron is
e!pressed in terms of a probability distribution, so one speaks of the probability that an
electron will be found at a particular location near a nucleus. The probability distribution,
in turn, is determined by a mathematical function known as a wavefunction, denoted I.
Wavefunctions for the distribution of particles are a general feature of quantum
mechanics, and for electrons in atoms they are known as atomic orbitals. The name
orbital is intended to e!press a distribution that is less precise than the e!plicit orbits of
the 8ohr model. The probability of finding an electron at a specified location is
proportional to the square of the amplitude of the wavefunction at that point. ence, the
sign 1positive or negative2 of the orbital is not relevant to the location of the electron,
because taking the square of I eliminates any negative sign it may have. owever, as
e!plained below in The quantum mechanics of bonding> $olecular orbital theory, the
sign is of crucial importance in the discussion of bonding between atoms and so cannot
be ignored.
Atomic structure and bonding Atomic structure The quantum mechanical model
Quantum numbers
Three quantum numbers are needed to specify each orbital in an atom, the most important
of these being the principal quantum number, n, the same quantum number that 8ohr
introduced. The principal quantum number specifies the energy of the electron in the
orbital, and, as n increases from its lowest value - through its allowed values 2, ;, . . . ,
the energies of the corresponding orbitals increase. The ground state, or lowest energy
state of the hydrogen atom, is the state in which it is normally found and has n G -, it
consists of a single electron in the orbital closest to the nucleus. #s n increases, so does
the average distance of the electron from the nucleus, and, as n approaches infinity, the
average distance also approaches infinity. The energy required to elevate the electron
from the orbital with n G - to the orbital with n G J is called the ioni&ation energy of the
hydrogen atom< this is the energy required to remove the electron completely from the
atom.
The quantum number n labels the shell of the atom. 5ach shell consists of n
2
individual
orbitals with the same principal quantum number and hence 1in the hydrogen atom2 the
same energy. 8roadly speaking, each shell consists of orbitals that lie at appro!imately
the same distance from the nucleus. The shells resemble the layers of an onion, with
successive shells surrounding the inner shells.
The ne!t quantum number needed to specify an orbital is denoted l and called the orbital
angular momentum quantum number. This quantum number has no role in determining
the energy in a hydrogen atom. It represents the magnitude of the orbital angular
momentum of the electron around the nucleus. In classical terms, as l increases, the rate
at which the electron circulates around the nucleus increases. The values of l in a shell of
principal quantum number n are limited to the n values 0, -, 2, . . . , n @ -, and the value
of l of an orbital in a given shell determines the subshell to which that orbital belongs. It
follows from the allowed values of l that there are n subshells in a shell of principal
quantum number n. #s will be e!plained, there are 2l ? - orbitals in a given subshell.
#lthough subshells are uniquely specified by the values of n and l, it is conventional to
label them in a slightly different manner. # subshell with l G 0 is called an s subshell, one
with l G - is called a p subshell, and one with l G 2 is called a d subshell. %ther subshells
are encountered, but these three are the only ones that need to be considered here. The
three subshells of the shell with n G ;, for e!ample, are called the ;s, ;p, and ;d
subshells.
#s noted above, a subshell with quantum number l consists of 2l ? - individual orbitals.
Thus, an s subshell 1l G 02 consists of a single orbital, which is called an s orbital< a p
subshell 1l G -2 consists of three orbitals, called p orbitals< and a d subshell 1l G 22
consists of five orbitals, called d orbitals. The individual orbitals are labeled with the
magnetic quantum number, ml, which can take the 2l ? - values l, l @ -, . . . , @l. The
orbital occupied in the lowest energy state of the hydrogen atom is called a -s orbital,
signifying that it belongs to 1and is in fact the only member of2 the shell with n G - and
subshell with l G 0.
!tomic structure and bonding !tomic structure &hapes of atomic orbitals
The atomic orbitals differ in shape. That is, the electrons they describe have different
probability distributions around the nucleus. Indeed, a part of the reason why orbitals
differ in energy is that the electrons that occupy them are likely to be found in different
regions around the parent nucleus and hence e!perience the latter4s attraction with
different strengths. The fact that all orbitals of a given shell in the hydrogen atom have
the same energy despite having different shapes is surprising and is associated with a
cancellation of different contributions to the energy. 1This so/called degeneracy, the
possession of the same energy by different wavefunctions, is also associated with the
coincidental numerical agreement of 8ohr4s model with e!periment.2 #s soon as a second
electron is present, however, the degeneracy is lost.
#ll s orbitals are spherically symmetrical. That is, an electron that occupies an s orbital
can be found with the same probability at any orientation 1at a given distance2 from the
nucleus. These orbitals are therefore represented by a spherical boundary surface 1)igure
2 2, which is a surface that captures a high proportion of the electron
density. The electron is more likely to be found somewhere inside the spherical boundary
surface than outside it.
When an electron is described by the wavefunction corresponding to a particular orbital,
the electron is said to occupy that orbital. In the ground state of a hydrogen atom, the
electron occupies the -s orbital, while in an e!cited state it occupies one of the other
orbitals to which it has moved. # unique feature of an s orbital is that an electron that
occupies it may be found right at the nucleus. #ll other orbitals have &ero amplitude at
the nucleus, and an electron that occupies one of them has &ero probability of being found
there. This apparently slight detail has remarkable consequences> it is largely responsible,
for instance, for the structure of the periodic table and hence for the pattern of the
compounds that the elements can form and for the properties of the substances that make
up the tangible world. (everal apparently trivial differences of this kind are responsible
for the richly varied properties of matter.
The boundary surfaces of the p orbitals are shown in )igure ; . #ll p
orbitals are double/lobed, with a region of high electron density on each side of the
nucleus. The boundary surface of a p orbital therefore consists of two lobes pro'ecting
from the nucleus. The three p orbitals of a given shell are often designated px, py, or pz
according to the alignment of their lobes along one of three mutually perpendicular a!es.
# d orbital has its lobes arranged in a slightly more complicated pattern and labeled
accordingly 1)igure : 2. #s indicated above and as suggested by the shape
of the boundary surfaces for p and d orbitals, neither p orbitals nor d orbitals have any
amplitude at the nucleus, and so an electron that occupies one of them will never be
found at that location in space.
!tomic structure and bonding !tomic structure The building'up principle
ydrogen and helium. The atomic orbitals of hydrogen are used as a basis for the
discussion of the structures of many/electron atoms. # simple qualitative account of their
use is presented here, without discussing the sophisticated, computer/based calculations
that are needed to achieve good agreement with e!periment> such agreement can be
obtained with the appropriate methods, and highly accurate energies can be calculated.
The procedure described in the following paragraphs is called the building/up 1or
sometimes, as in the original +erman, #ufbau2 principle.
In the building/up principle, Z electrons 1for a neutral atom of an element of atomic
number Z2 are placed in succession into an array of hydrogen/like atomic orbitals in such
a way as to achieve the lowest possible total energy. Thus, to account for the structure of
a helium atom 1for which Z G 22, one electron is allowed to occupy a hydrogen/like -s
orbital, and then a second electron is allowed to 'oin it, giving the electron configuration
-s
2
1which is read Eone/s/twoF2.
Atomic structure and bonding Atomic structure The buildingup principle !ithium
through neon
To produce the ground/state electron configuration of the ne!t element, lithium 1Z G ;2,
one more electron is added. owever, that electron cannot occupy the -s orbital, for it has
a property known as spin, which is fundamental to its behaviour. (pin is an intrinsic
property of an electron, like its mass or charge. In elementary treatments, spin is often
visuali&ed as an actual spinning motion. owever, it is a quantum mechanical property
without a classical counterpart, and to picture spin in this way can be misleading.
9evertheless, for the present discussion, such a picture is useful. #n electron has a fi!ed
amount of spin, in the sense that every electron in the universe is continually spinning at
e!actly the same rate. #lthough the spin of an electron is constant, the orientation of the
a!is of spin is variable, but quantum mechanics restricts that orientation to only two
possibilities. The two possible spin states of an electron are represented by the arrows K
and L and are distinguished by the spin magnetic quantum number, ms, which takes the
values ?
-
M2 1for the K spin2 or @
-
M2 1for the L spin2.
8ecause of its spin, an electron must obey a fundamental requirement known as the Aauli
e!clusion principle. This principle 1which is a consequence of the more fundamental
Aauli principle2 states that no more than two electrons may occupy a given orbital and, if
two electrons do occupy one orbital, their spins must be paired 1denoted K L< that is, one
electron must be K and the other must be L2. The Aauli e!clusion principle is responsible
for the importance of the electron pair in the formation of covalent bonds. It is also, on a
more cosmic scale, the reason why matter has bulk< that is to say, all electrons cannot
occupy the orbitals of lowest energy but are instead located in the many shells that are
centred on the nucleus. #lso owing to the e!istence of spin, two ob'ects do not simply
blend into one another when they are in contact< the electrons of ad'acent atoms cannot
occupy the same space, thereby prohibiting the combining of two atoms into one. ere
again is an e!ample of a seemingly trivial property, in this case spin, having
consequences of profound and macroscopic importance. In this instance, the spin of the
electron is responsible for the e!istence of identifiable forms of matter.
With the Aauli e!clusion principle in mind, one can see that in helium the -s orbital 1and
hence the entire n G - shell, for that shell consists of only a single orbital2 is full. The
helium atom is said to be a closed/shell species. There is an obvious connection between
the remarks made earlier concerning the inertness of helium and the fact that its valence
shell is complete. The details of this connection will be considered below. With the n G -
shell complete, the third electron of lithium must enter an orbital of the ne!t higher shell,
that with n G 2. This shell consists of two subshells, which are composed of the single 2s
orbital and the three 2p orbitals, respectively.
The ne!t problem that must be addressed is the e!perimental 1i.e., spectroscopic2 fact that
the third electron occupies the 2s orbital rather than any of the three 2p orbitals to give
the configuration -s
2
2s
-
. In a hydrogen atom all the orbitals of a shell are degenerate.
That is not the case, however, in atoms where more than one electron is present< in such
instances, within a given shell the s subshell lies at lower energy than the p subshell. The
lower energy of an ns orbital relative to that of an np orbital arises from the ability of an s
electron to be found e!tremely close to the nucleus.
If the electrons in ns and np orbitals were distributed equally outside the closed shells that
constitute the helium/like core of the atom, then they would be equally repelled by the
two core electrons. #s a result, they would e!perience a lower effective nuclear charge,
the difference between the true charge of the nucleus and the net charge e!perienced after
allowing for the repulsion of any electrons present. The reduction of the actual nuclear
charge by the effect of the other electrons in the atom is referred to as the shielding of the
nuclear charge. 9e!t, it is necessary to note that a 2s electron can penetrate through the
core 1that is, have non&ero probability of being found closer to the nucleus than the bulk
of the core electron density2. If penetration occurs, the electron e!periences the full
nuclear charge and hence has a lower energy than an electron in an orbital that cannot
penetrate through the shielding core. It is this combination of the effects of penetration
and shielding that results in an ns orbital having a slightly lower energy than an np
orbital, for the latter has &ero amplitude at the nucleus.
It follows from this discussion that, for a lithium atom to achieve the lowest possible
energy, the third electron should occupy the 2s orbital, in accord with spectroscopic
evidence. (uccessive elements complete first the 2s subshell 1at beryllium, 8e< Z G :2 and
then begin the 2p subshell. The three orbitals of the 2p subshell are completed after the
addition of si! more electrons, which occurs at neon 19e< Z G -02.
#nother aspect of the building/up principle needs to be mentioned at this point, although
its significance will not become fully apparent until later. When there are several orbitals
of the same energy available for occupation, the electron configurations observed in
atoms are found to be reproduced if und4s rule is adopted. This rule states that, if more
than one orbital is available for occupation by the electrons currently being
accommodated, then those electrons occupy separate orbitals and do so with parallel
spins 1both K, for instance, which would be denoted KK2. The occupation of separate
orbitals minimi&es the repulsion energy between the electrons and hence leads to a lower
energy than if they were confined to the same region of space. The requirement of und4s
rule that the electrons have parallel spins is more subtle. When electrons have parallel
spins, they are constrained by quantum mechanics to stay apart from one another< as a
result the atom can shrink slightly and hence improve the energy of attraction between its
electrons and nucleus.
#t neon the entire n G 2 shell is complete. #t this point it should be noticed that the
second noble gas, neon, has a closed/shell electron configuration, as does the first noble
gas, helium. 9ote also that eight electrons are needed to pass from helium to neon, that
eight is the ma!imum number of electrons that the n G 2 shell can accommodate, and that
there are eight columns of elements in the main part of the periodic table. Thus, a
combination of the Aauli e!clusion principle and the effects of penetration and shielding
has e!plained the essential structure of this table.
Atomic structure and bonding Atomic structure The buildingup principle "odium
through argon
The element that follows neon in the periodic table is sodium 19a2, with Z G --. Its
additional electron is e!cluded by the Aauli principle from neon4s closed shell and must
enter the ne!t higher energy shell, in which n G ;. This shell contains three subshells, ;s,
;p, and ;d, and, as a result of the effects of penetration and shielding, the energies of
these subshells lie in the order ;s N ;p N ;d. It follows that the incoming electron enters
the ;s orbital, resulting in the ground/state electron configuration of a sodium atom being
O9eP;s
-
, where O9eP represents the neon/like -s
2
2s
2
2p
7
closed shell. It is a striking feature
of this discussion that the electron configuration of sodium is the e!act analogue of the
electron configuration of lithium 10i2, OeP2s
-
, with its helium/like closed/shell core.
$oreover, sodium belongs to the same family as lithium and has strikingly similar
chemical properties, including the ability to form ionic compounds that contain singly/
charged cations, namely 9a
?
and 0i
?
, respectively.
The third row of the periodic table 1sodium through argon2 is in fact a replication of the
second row 1lithium through neon2, the only difference being that a more distant shell of
s and p orbitals 1the shell with n G ;2 is being occupied. The elements of this row bear a
strong family resemblance, particularly in terms of their valences, to the elements directly
above them in the second row. $oreover, after eight members, the row terminates at the
noble gas argon, with a closed set of ;s and ;p subshells.
Atomic structure and bonding Atomic structure The buildingup principle #otassium
through $rypton
*hemistry, though, is a subtle sub'ect, and its variety depends on that subtlety. The detail
needed at this point 1but which will not be unduly dwelt upon2 is that the effects of
penetration and shielding are so pronounced that the :s orbital is so substantially lowered
in energy by its ability to penetrate close to the nucleus that it lies lower than the ;d
orbitals, even though those orbitals belong to a shell of lower principal quantum number.
Thus, after argon, the ne!t electron enters the :s orbital, not a ;d orbital, giving the
configuration O#rP:s
-
for potassium, where O#rP represents the configuration of argon.
Indeed, potassium is similar in chemical properties to sodium, which is consistent with its
analogous electron configuration.
*alcium is the ne!t element after potassium, and its additional electron completes the :s
subshell. #t this point the five ;d orbitals are ne!t in line for occupation, and their
successive filling accounts for the -0 elements 1from scandium to &inc2 that are classified
as transition elements. %nly after the ;d subshell is complete are the :p orbitals in line for
occupation, and then si! electrons are needed to bring the elements to the ne!t noble gas,
krypton. The presence of the ;d orbitals in the scheme of occupation lengthens the fourth
row of the periodic table from . to -. members, and the row from potassium to krypton is
called the first long period of the periodic table.
The pattern suggested by this discussion now continues as electrons are added, and the
ne!t row of the table replicates the electron configurations of the fourth row. The general
pattern of the periodic table is now established.
!tomic structure and bonding (eriodic arrangement and trends
!rrangement of the elements
The columns of the periodic table, which contain elements that show a family
resemblance, are called groups. #ll members of a particular group have analogous
outermost 1valence2 electron configurations, suggesting that all members of a group
should show a family relationship in the types and numbers of the chemical bonds that
they are able to form. The hori&ontal rows of the periodic table are called periods. 5ach
period corresponds to the successive occupation of the orbitals in a valence shell of the
atom, with the long periods corresponding to the occupation of the orbitals of a d
subshell. (uccessive periods down the table correspond to successively higher values of n
for the valence shell. The first period 1consisting of only hydrogen and helium2
corresponds to n G -, the second period 1from lithium to neon2 to n G 2, and so on. These
successive periods correspond to atoms in which the valence shell is outside a more
electron/rich core of inner completed shells. 5ach of the first si! periods terminates at a
noble gas, with a closed/shell electron configuration. The replication of analogous
electron configurations that characteri&es the periodic table is an e!ample of the
periodicity of the elements and is responsible for the overall pattern of the elements when
arranged as $endeleyev, with chemical insight and without the benefit of quantum
mechanics, had originally proposed.
!tomic structure and bonding (eriodic arrangement and trends (eriodic
trends in properties
The elements show a rich variety of periodicities. 5mphasis will be placed on the
periodicity of the properties that are of direct relevance to the formation of chemical
bonds. These properties are essentially the si&e of atoms and the energy required to
remove electrons from or attach them to neutral atoms.
Atomic structure and bonding #eriodic arrangement and trends #eriodic trends in
properties Atomic si%e
8roadly speaking, the radii of atoms increase from the top to the bottom of the periodic
table and decrease from left to right. ence, the largest atoms are found at the lower left
of the table, and the smallest ones are found at the upper right. The increase in radius
down each group stems from the fact that in successive periods one more layer of the
atomic EonionF is being formed< that is, electrons are being added to a new shell outside a
closed/shell core of the atom. Thus, lithium consists of one electron outside a compact,
helium/like core, sodium consists of a single electron outside a neon/like core 1which
itself has a helium/like core deep within its structure2, and so on down the group.
The decrease in atomic radius from left to right across a period is perhaps more
surprising, for a contraction in si&e occurs despite the presence of more electrons in each
successive element. Thus, lithium has three electrons, and beryllium 18e2 has four, but
beryllium is slightly smaller than lithium. )luorine, with nine electrons, might be
e!pected to be a significantly larger atom than lithium, but the opposite is true. The
e!planation of this seemingly counterintuitive trend is that, although successive elements
have a larger number of electrons, they also have a higher nuclear charge because of the
increasing number of protons. That positive charge draws in the surrounding electrons to
make the atom more compact. The inner/shell, or core, electrons, which do not increase
upon going across a period, effectively shield the outer/shell electrons from the positive
charge of the nucleus. The outer/shell electrons that are added upon going across a
period, however, do not shield other valence electrons from the increasing charge of the
nucleus as well as the core electrons do. Thus, the outer/shell electrons are pulled in more
closely by the greater charge of the nucleus. There is clearly competition 1as is so often
the case in chemistry2 between the inflating effects of the presence of more electrons and
the contracting effects of the stronger nuclear charge. With a few e!ceptions, the latter
influence dominates slightly, and successive atoms are smaller on moving across a
period.
Ions, both cations and anions, show a similar variation in si&e with the position of their
parent elements in the periodic table. owever, there are two gross differences. )irst,
cations 1which are formed by the loss of electrons from the valence shell of the parent
atom2 are invariably smaller than their parent atoms. In some cases the difference can be
considerable 1more than Q0 percent2. In effect, the outer layer of the atomic EonionF is
discarded when the valence electrons are lost, so the radius of the cation is that of the
compact atomic core.
#nions, which are formed by the gain of electrons by an atom"most commonly into the
incomplete valence shell"are invariably larger than the parent atoms. In this case, the
additional electrons repel the electrons that are already present, and the entire atom
inflates.
Atomic structure and bonding #eriodic arrangement and trends #eriodic trends in
properties Ioni%ation energy
9e!t in order of importance for determining the number and type of chemical bonds that
an atom may form is the ioni&ation energy of the element. It is the minimum energy
needed to remove an electron from an atom of the element. The energy is required
because all the electrons of an atom are attracted by the positive charge of the nucleus,
and work must be done to drag the electron off the atom to produce a cation. *hemical
bond formation stems from the transfer or sharing of electrons, and so the energy required
to remove an electron is a crucial criterion in the ability of an atom to form a bond.
In broad terms, the variation of ioni&ation energies throughout the periodic table mirrors
the variation in atomic radii, with small atoms typically having high ioni&ation energies
and large atoms usually having small ones. Thus, the elements with the lowest ioni&ation
energies 1and hence from which an electron is most readily removed2 are found at the
lower left of the periodic table, near cesium and francium, and elements with the highest
ioni&ation energies are found at the upper right of the table, close to fluorine and helium.
The variation in ioni&ation energy correlates with the variation in atomic radius because a
valence electron in a bulky atom is on average far from the nucleus and therefore
e!periences only a weak attraction to it. %n the other hand, a valence electron in a small
atom is close to its parent nucleus and is sub'ect to a strong attractive force.
#t this point the relative inertness of the noble gases can be in part e!plained. They lie on
the right of the periodic table, and the members of the family that are closest to helium
1namely, neon and argon2 have among the highest ioni&ation energies of all the elements.
Thus, their electrons are not readily available for bond formation. %nly lower in the
group, at krypton and !enon, do the ioni&ation energies become comparable to those of
other elements, and these elements can be coa!ed into compound formation by
sufficiently aggressive reagents 1most notably by fluorine2.
#n important feature of the ioni&ation energy is that the energy required to remove a
second electron from an atom is always higher than the energy needed to remove the first
electron. %nce an electron has been removed, there are fewer electrons to repel one
another in the cation, so more work must be done to drag the ne!t electron away from the
nucleus. The same is true of the third electron, which is even less available than the
second electron. owever, an important point is that, if an electron needs to be removed
from the core of the atom 1as is the case for a second electron removed from sodium2,
then the ioni&ation energy may be e!ceedingly high and not attainable in the course of a
typical chemical reaction 1as will be 'ustified below2. The reason for the high ioni&ation
energies of core electrons is largely that these electrons lie much closer to the nucleus
than do the valence electrons, and thus they are gripped by it much more strongly.
It is a general rule that for elements on the left in the periodic table, which have one, two,
or three electrons in their valence shells, sufficient energy is attainable in chemical
reactions for their removal, but not enough energy is available for removing any electrons
from inner shells. ence, sodium can form 9a
?
ions, magnesium can form $g
2?
ions, and
aluminum can form #l
;?
ions.
%ne reason for the importance of noble gas configurations in chemical bond formation
now becomes apparent. %nce a noble gas, closed/shell configuration is obtained, the
ready removal of electrons to form cations ceases 1as does the opportunity for the partial
removal of electrons for the sharing required in the formation of covalent bonds, as
discussed below2. # large energy barrier is encountered when going beyond the removal
of the valence electrons of an atom.
Ioni&ation energies do not correlate with atomic radii e!actly, because there are other
influences beyond the distance of the electron from the nucleus that determine the energy
needed to remove an electron. These influences include the details of the occupation of
the orbitals in the valence shell. %nce again, the origin of a further possibility for
competition becomes apparent, in this case between effects that stem from si&e alone and
those that are determined by the energy requirements for ioni&ation.
Atomic structure and bonding #eriodic arrangement and trends #eriodic trends in
properties Electron affinity
Third in importance for bond formation after si&e and ioni&ation energy is the energy
change accompanying the attachment of electrons to a neutral atom. This energy is
e!pressed as the electron affinity, which is the energy released when an electron is
attached to an atom of the element. In many cases, the electron affinity is positive,
signifying that energy is indeed released when an electron attaches to an atom. (uch is
the case when the incoming electron enters a vacancy in the valence shell of the atom.
#lthough it is repelled by the electrons already present, it is sufficiently close to the
nucleus for there to be a net attraction. ence, the energy of the electron is lower when it
is a part of the atom than when it is not. owever, if the incoming electron has to start a
new shell because the orbitals of the neutral atom are full, then it remains so far from the
nucleus and so strongly repelled by the electrons already present that there is a net
repulsion, and energy must be supplied to attach the electron to form an anion. In such
cases, the electron affinity is negative.
ere lies the second part of the overall reason why a noble gas configuration is the end of
the road for the formation of ions"in this case anions. %nce the noble gas configuration
has been attained, there may be serious energy disadvantages in the attachment of
additional electrons. Thus, a chlorine atom can accept one electron to complete its
valence shell, and *l
@
is a common species. #n o!ygen atom can accept two electrons to
complete its shell, and %
2@
is also common. These remarks conceal certain difficulties,
but they are broadly true and account for the formation of the anions characteristic of the
elements located on the right in the periodic table.
5lectron affinities vary through the periodic table, and their periodicity is more comple!
than that of ioni&ation energies. 8roadly speaking, however, electron affinities are largest
close to the upper right of the periodic table near fluorine. 1#s indicated above, the
closed/shell noble gases have lower electron affinities.2
In summary, the low ioni&ation energies and low electron affinities of the elements on the
lower left of the periodic table account for the readiness of their atoms to form cations.
They also correlate, as discussed below, with the fact that these elements are metallic, for
that property depends on the ready loss of electrons. %n the other hand, the high
ioni&ation energies and high electron affinities of elements on the upper right of the
periodic table 1with the e!ception of the noble gases2 account for their ready formation of
anions 1and for the fact that they are generally nonmetals, since that property is
associated with the difficulty of removing electrons from atoms2.
Atomic structure and bonding #eriodic arrangement and trends #eriodic trends in
properties Electronegativity
This synoptic view of ion formation is summari&ed by the concept of electronegativity, R.
There are numerous definitions of electronegativity. Sualitatively, the electronegativity of
an element is the ability of one of its atoms to attract electrons toward itself when it is
part of a compound 1this definition was originally proposed by the #merican chemist
0inus Aauling2. (uch an ability is high if the ioni&ation energy of the element is high 1so
that the atom is reluctant to give up electrons2 and if its electron affinity is also high 1for
then it is energetically favourable for it to acquire electrons2. It follows that atoms with
high electronegativities are those in the upper right/hand corner of the periodic table,
close to fluorine 1but e!cluding the noble gases2. (uch elements are likely to form anions
when they form compounds. 5lements with low ioni&ation energies 1so that they readily
give up electrons2 and low electron affinities 1so that they have little tendency to acquire
electrons2 have low electronegativities 1i.e., they are electropositive2 and occur at the
lower left of the periodic table. (uch elements are likely to form cations during
compound formation. 1The effect of electronegativity on the polarity of a bond is
discussed below in the section The polarity of molecules.2
5mphasis has been placed on ion formation in this section, and hence it may appear that
covalence was unduly neglected. owever, the scene is now set for an introduction to the
whole range of bonding types, and it will be e!plained how the atomic property of
electronegativity helps to unify the discussion.
Bonds between atoms
It has been shown that, for reasons related to the energy requirements for electron
removal or addition, only the electrons in valence shells play a significant role in the
formation of bonds between atoms. enceforth this article will concentrate on these
electrons alone. 0ewis introduced the conventions of representing valence electrons by
dots arranged around the chemical symbol of the element, as in T, 9aT, and .*l>.... , and
of discussing bond formation as the transfer of dots from one symbol to another. This
seemingly simplistic device turns out to be very useful for establishing the characteristics
of chemical bonds and will be e!amined in this section.
%onds between atoms The formation of ionic bonds $ewis formulation of an
ionic bond
In 0ewis terms, the formation of an ionic bond stems from the transfer of electrons from
one atom to another. When such a transfer occurs, all the valence electrons on the more
electropositive element 1from one of the first three groups on the left in the periodic
table2 are removed to e!pose the core of the atom. The electrons so released are accepted
into the empty orbitals of the valence shell of the more electronegative atom 1typically
from the groups immediately to the left of the noble gases2< the valence shell is thereby
filled. Thus, the formation of the ionic compound sodium chloride can be represented by
the following process>
The formation of aluminum o!ide 1alumina2 involves selecting enough aluminum and
o!ygen atoms to ensure that all the electrons released by the aluminum atoms 1three from
each one2 are accommodated by o!ygen atoms 1each of which can accept two electrons2>

1The numbers of atoms required to balance the electrons donated and accepted is
indicated by the chemical formula #l2%; for aluminum o!ide.2
That the transfer of electrons represented by these diagrams leads to a lowering of energy
can be checked by assessing the energies associated with them. There is more to the
process than a straightforward consideration of ioni&ation energy and electron affinity.
The ioni&ation energy of sodium is larger than the electron affinity of chlorine, so energy
is required to remove an electron from a sodium atom and attach it to a chlorine atom.
That is, at first sight it appears that the total energy of a 9a
?
ion and a *l
@
ion is greater
than that of a sodium atom and a chlorine atom. If that were the case, then it would be
hard to understand how sodium chloride could be a stable species relative to a gas of
sodium and chlorine atoms.
There are in fact two errors in such a simple approach. )irst, the argument has ignored the
favourable energy of interaction between the cation and the anion. The net energy of
formation of a 9a
?
ion and a *l
@
ion is the sum of three terms. The first is the energy
investment needed to ioni&e a sodium atom. The second is a somewhat smaller energy
that is released when the electron from the sodium atom attaches to a chlorine atom. #t
this stage, the net energy change is positive, indicating a higher energy than for the two
atoms. owever, because there is an attraction between opposite charges, there is a
further release of energy as a result of the interaction of the two ions. This additional
favourable contribution to the energy varies with the separation of the ions and
strengthens as the two ions approach one another. Thus, at large separations the neutral
atoms have the lowest energy, but as the two atoms are brought together a point is
reached at which the lowest total energy is obtained if an electron transfers from the
sodium atom to the chlorine atom. #t this distance, and at shorter distances, 9a
?
*l
@
is the
lower/energy species.
The second feature omitted from the argument is that an ionic compound does not consist
of an isolated cation and anion. #n ionic compound is typically a solid formed from an
array of alternating cations and anions. The packing of ions together and their
electrostatic interactions with one another account for the typical features of ionic
compounds"namely, their brittleness and high melting points. $oreover, when studying
the stability of such compounds, one should more appropriately consider the energy
changes associated with their formation from the elements in their standard state 1such as
solid metallic sodium and gaseous chlorine molecules2 than from a gas of atoms of the
elements.
%onds between atoms The formation of ionic bonds The %orn'Haber cycle
The analysis of the formation of an ionic compound from its elements is commonly
discussed in terms of a 8orn/aber cycle, which breaks the overall process into a series
of steps of known energy. The 8orn/aber cycle for the formation of sodium chloride is
shown in )igure Q . #t the start of the cycle, the elements are considered to
be in the form in which they e!ist at normal pressure and temperature. )irst, sodium
metal is vapori&ed to a gas of sodium atoms. This step requires an input of energy known
as the atomi&ation energy of sodium metal. 9e!t, the appropriate number of chlorine
molecules 1*l22 are broken apart to provide a gas of chlorine atoms. This step also
requires a considerable input of energy that is called the dissociation energy of chlorine.
The origin of these two contributions to the energy can be clarified by considering
metallic and covalent bonding in more detail 1specifically, the lowering of energy that
occurs when metallic or covalent bonds form2< here they can be treated as empirical
quantities. #t this stage, an electron is removed from each sodium atom and attached to
each chlorine atom. The ioni&ation requires a considerable input of energy, and a fraction
of that investment is recovered from the electron affinity of the chlorine atoms. %verall,
however, there is a considerable increase in energy as compared to the two starting
materials.
#t this stage, the ions are allowed to come together to form a crystalline array. This step
releases a large quantity of energy called the lattice energy of the compound. 5nergy is
released in the process of crystal formation because first a cation becomes surrounded by
anions, then that cluster of anions becomes surrounded by cations, and so on. #s a result
of this packing, every cation has anions as neighbours, and every anion has cations
around it, and there is a strong overall attractive interaction among the many ions of
opposite charge in the crystal. )or sodium chloride, the lattice energy is so great that
more energy is released in this step than is required for all the preceding steps combined,
and solid sodium chloride therefore has a lower energy than sodium metal and chlorine
gas. It is for this reason that, when sodium reacts with chlorine, a large quantity of heat is
released.
%onds between atoms The formation of ionic bonds Factors favouring ionic
bonding
# 8orn/aber cycle gives an indication of the factors that favour ionic bonding. %verall,
the lattice energy must be great enough to overcome the energy required for ion
formation. It follows that only elements with reasonably low ioni&ation energies can
contribute, as cations, to ionic materials, for too large an ioni&ation energy could not be
recovered from the resulting lattice energy. In practice, this criterion means that only
metallic elements are likely to form cations, and two elements are unlikely to form an
ionic compound unless one of them is a metal. $oreover, the steep increase in ioni&ation
energy required to break into a closed shell precludes the loss of all but the valence
electrons. )urthermore, no more than about three electrons per atom can be lost before
the increase in ioni&ation energy becomes prohibitive.
It can also be seen from the 8orn/aber cycle that elements will contribute anions to an
ionic compound only if their electron affinity is positive or, at least, not too strongly
negative. 5lements with positive electron affinities are likely to form anions 1as long as a
metal is present2. # negative electron affinity can be tolerated provided it is not too great
and the additional energy investment can be recovered from a greater lattice energy. That
is the reason why ionic o!ides are so common> although energy is required to push the
second electron on an o!ygen atom to make an %
2@
ion, the resulting ion produces such a
high lattice energy that the energy investment is overcome.
Ionic bonding is likely to occur if the lattice energy of the compound is large, for a large
lattice energy can compensate for some strongly demanding energy requirements, most
notably for cation formation, earlier in the cycle. igh lattice energies are achieved if the
ions that form the lattice are small and highly charged, for small ions can pack together
closely and interact strongly with one another. The %
2@
ion of o!ides is small 1o!ygen lies
well to the right in the periodic table2 and is reasonably highly charged 1it has two
negative charges< three negative charges is about the limit for monatomic anions2. #s a
result, ionic o!ides are widely formed by metallic elements. #lthough it is conceivable
that %
;@
ions could be formed if enough energy were provided to overcome the repulsion
from the many electrons present in %
2@
, the necessary energy would not be recovered
from the lattice energy, for %
;@
anions are so large that the lattice energy of any
compound they would form would be small. %nce again, the termination of electron gain
at a noble gas configuration is not so much a sign of some magic stability of such a
species but rather a consequence of the fact that after such a configuration has been
attained there is insufficient opportunity for achieving a lower energy.
The actual pattern in which cations and anions pack together is the one that results in the
greatest lattice energy 1that is, the greatest lowering of energy of the ions relative to the
gas of ions2. )or further details on crystal arrangements, see crystal.
&onds between atoms 'ovalent bonds
When none of the elements in a compound is a metal, no atoms in the compound have an
ioni&ation energy low enough for electron loss to be likely. In such a case, covalence
prevails. #s a general rule, covalent bonds are formed between elements lying toward the
right in the periodic table 1i.e., the nonmetals2. $olecules of identical atoms, such as 2
and buckminsterfullerene 1*702, are also held together by covalent bonds.
%onds between atoms #ovalent bonds $ewis formulation of a covalent bond
In 0ewis terms a covalent bond is a shared electron pair. The bond between a hydrogen
atom and a chlorine atom in hydrogen chloride is formulated as follows>

In a 0ewis structure of a covalent compound, the shared electron pair is represented by a
line, so the 0ewis structure of hydrogen chloride is denoted *l>.... . The electron pair
represented by the line is called a bonding pair< the three other pairs of electrons on the
chlorine atom are called lone pairs and play no direct role in holding the two atoms
together.
5ach atom in the hydrogen chloride molecule attains a closed/shell octet of electrons by
sharing and hence achieves a ma!imum lowering of energy. In general, an incomplete
shell means that some attracting power of a nucleus may be wasted, and adding electrons
beyond a closed shell would entail the energetic disadvantage of beginning the ne!t shell
of the atom concerned. 0ewis4 octet rule is again applicable and is seen to represent the
e!treme means of achieving lower energy rather than being a goal in itself.
# covalent bond forms if the bonded atoms have a lower total energy than the widely
separated atoms. The simplest interpretation of the decrease in energy that occurs when
electrons are shared is that both electrons lie between two attracting centres 1the nuclei of
the two atoms linked by the bond2 and hence lie lower in energy than when they
e!perience the attraction of a single centre. This e!planation, however, requires
considerable modification to capture the full truth about bonding, and it will be discussed
further below when bonding is considered in terms of quantum mechanics.
0ewis structures of more comple! molecules can be constructed quite simply by
e!tending the process that has been described for hydrogen chloride. )irst, the valence
electrons that are available for bonding are counted 12 U - ? 7 G . in 2%, for e!ample,
and : ? : U V G ;2 in carbon tetrachloride, **l:2, and the chemical symbols for the
elements are placed in the arrangement that reflects which are neighbours>

9e!t, one bonding pair is added between each linked pair of atoms>

The remaining electrons are then added to the atoms in such a way that each atom has a
share in an octet of electrons 1this is the octet/rule part of the procedure2>

)inally, each bonding pair is represented by a dash>
19ote that 0ewis structures do not necessarily show the actual shape of the molecule,
only the topological pattern of their bonds.2
In some older formulations of 0ewis structures, a distinction was made between bonds
formed by electrons that have been supplied by both atoms 1as in @*l, where one shared
electron can be regarded as supplied by the hydrogen atom and the other by the chlorine
atom2 and covalent bonds formed when both electrons can be regarded as supplied by one
atom, as in the formation of %
@
from %
2@
and
?
. (uch a bond was called a coordinate
covalent bond or a dative bond and symboli&ed % W
@
. owever, the difficulties
encountered in the attempt to keep track of the origin of bonding electrons and the
suggestion that a coordinate covalent bond differs somehow from a covalent bond 1it does
not2 have led to this usage falling into disfavour.
%onds between atoms #ovalent bonds !dvanced aspects of $ewis structures
The 0ewis structures illustrated so far have been selected for their simplicity. # number
of elaborations are given below.
&onds between atoms 'ovalent bonds Advanced aspects of !ewis structures Multiple
bonds
)irst, an atom may complete its octet by sharing more than one pair of electrons with a
bonded neighbour. Two shared pairs of electrons, represented by a double dash 1G2, form
a double bond. ,ouble bonds are found in numerous compounds, including carbon
dio!ide>
Three shared pairs of electrons are represented by a triple dash 1X2 and form a triple bond.
Triple bonds are found in, for e!ample, carbon mono!ide, nitrogen molecules, and
acetylene, shown, respectively, as>
# double bond is stronger than a single bond, and a triple bond is stronger than a double
bond. owever, a double bond is not necessarily twice as strong as a single bond, nor is a
triple bond necessarily three times as strong. Suadruple bonds, which contain four shared
pairs of electrons, are rare but have been identified in some compounds in which two
metal atoms are bonded directly together.
&onds between atoms 'ovalent bonds Advanced aspects of !ewis structures
(esonance
There is sometimes an ambiguity in the location of double bonds. This ambiguity is
illustrated by the 0ewis structure for o&one 1%;2. The following are two possible
structures>
In such cases, the actual 0ewis structure is regarded as a blend of these contributions and
is written>
The blending together of these structures is actually a quantum mechanical phenomenon
called resonance, which will be considered in more detail below. #t this stage, resonance
can be regarded as a blending process that spreads double/bond character evenly over the
atoms that participate in it. In o&one, for instance, each o!ygen/o!ygen bond is rendered
equivalent by resonance, and each one has a mi!ture of single/bond and double/bond
character 1as indicated by its length and strength2.
&onds between atoms 'ovalent bonds Advanced aspects of !ewis structures
Hypervalence
0ewis structures and the octet rule 'ointly offer a succinct indication of the type of
bonding that occurs in molecules and show the pattern of single and multiple bonds
between the atoms. There are many compounds, however, that do not conform to the
octet rule. The most common e!ceptions to the octet rule are the so/called hypervalent
compounds. These are species in which there are more atoms attached to a central atom
than can be accommodated by an octet of electrons. #n e!ample is sulfur he!afluoride,
()7, for which writing a 0ewis structure with si! (@) bonds requires that at least -2
electrons be present around the sulfur atom>
1%nly the bonding electrons are shown here.2 In 0ewis terms, hypervalence requires the
e!pansion of the octet to -0, -2, and even in some cases -7 electrons. ypervalent
compounds are very common and in general are no less stable than compounds that
conform to the octet rule.
The e!istence of hypervalent compounds would appear to deal a severe blow to the
validity of the octet rule and 0ewis4 approach to covalent bonding if the e!pansion of the
octet could not be rationali&ed or its occurrence predicted. )ortunately, it can be
rationali&ed, and the occurrence of hypervalence can be anticipated. In simple terms,
e!perience has shown that hypervalence is rare in periods - and 2 of the periodic table
1through neon2 but is common in and after period ;. Thus, the octet rule can be used with
confidence for carbon, nitrogen, o!ygen, and fluorine, but hypervalence must be
anticipated thereafter. The conventional e!planation of this distinction takes note of the
fact that, in period/; elements, the valence shell has n G ;, and this is the first shell in
which d orbitals are available. 1#s noted above, these orbitals are occupied after the :s
orbitals have been filled and account for the occurrence of the transition metals in period
:.2 It is therefore argued that atoms of this and subsequent periods can utili&e the empty d
orbitals to accommodate electrons beyond an octet and hence permit the formation of
hypervalent species.
In chemistry, however, it is important not to allow mere correlations to masquerade as
e!planations. #lthough it is true that d orbitals are energetically accessible in elements
that display hypervalence, it does not follow that they are responsible for it. Indeed,
quantum mechanical theories of the chemical bond do not need to invoke d/orbital
involvement. These theories suggest that hypervalence is probably no more than a
consequence of the greater radii of the atoms of period/; elements compared with those
of period 2, with the result that a central atom can pack more atoms around itself. Thus,
hypervalence is more a steric 1geometric2 problem than an outcome of d/orbital
availability. ow si! atoms can be bonded to a central atom by fewer than si! pairs of
electrons is discussed below.
&onds between atoms 'ovalent bonds Advanced aspects of !ewis structures
Incompleteoctet compounds
0ess common than hypervalent compounds, but by no means rare, are species in which
an atom does not achieve an octet of electrons. (uch compounds are called incomplete/
octet compounds. #n e!ample is the compound boron trifluoride, 8);, which is used as
an industrial catalyst. The boron 182 atom supplies three valence electrons, and a
representation of the compound4s structure is>
The boron atom has a share in only si! valence electrons. It is possible to write 0ewis
structures that do satisfy the octet rule.
owever, whereas in the incomplete octet structure the fluorine atoms have three lone
pairs, in these resonance structures one fluorine atom has only two lone pairs, so it has
partly surrendered an electron to the boron atom. This is energetically disadvantageous
for such an electronegative element as fluorine 1which is in fact the most electronegative
element2, and the three octet structures turn out to have a higher energy than the
incomplete/octet structure. The latter is therefore a better representation of the actual
structure of the molecule. Indeed, it is e!actly because the 8); molecule has an
incomplete/octet structure that it is so widely employed as a catalyst, for it can use the
vacancies in the valence shell of the boron atom to form bonds to other atoms and thereby
facilitate certain chemical reactions.
&onds between atoms 'ovalent bonds Advanced aspects of !ewis structures Electron
deficient compounds
#nother type of e!ception to the 0ewis approach to bonding is the e!istence of
compounds that possess too few electrons for a 0ewis structure to be written. (uch
compounds are called electron/deficient compounds. # prime e!ample of an electron/
deficient compound is diborane, 827. This compound requires at least seven bonds to
link its eight atoms together, but it has only 2 U ; ? 7 U - G -2 valence electrons, which is
enough to form only si! covalent bonds. %nce again, it appears that, as in hypervalent
compounds, the e!istence of electron/deficient compounds signifies that a pair of
electrons can bond together more than two atoms. The discussion of the quantum
mechanical theory of bonding below shows that this is indeed the case.
# number of e!ceptions to 0ewis4 theory of bonding have been catalogued here. It has
further deficiencies. )or e!ample, the theory is not quantitative and gives no clue to how
the strengths of bonds or their lengths can be assessed. In the form in which it has been
presented, it also fails to suggest the shapes of molecules. )urthermore, the theory offers
no 'ustification for regarding an electron pair as the central feature of a covalent bond.
Indeed, there are species that possess bonds that rely on the presence of a single electron.
1The one/electron transient species 2
?
is an e!ample.2 9evertheless, in spite of these
difficulties, 0ewis4 approach to bonding has proved e!ceptionally useful. It predicts when
the octet rule is likely to be valid and when hypervalence can be anticipated, and the
occurrence of multiple bonds and the presence of lone pairs of electrons correlate with
the chemical properties of a wide variety of species. 0ewis4 approach is still widely used
as a rule of thumb for assessing the structures and properties of covalent species, and
modern quantum mechanical theories echo its general content.
The following sections discuss how the limitations of 0ewis4 approach can be overcome,
first by e!tending the theory to account for molecular shapes and then by developing
more thorough quantum mechanical theories of the chemical bond.
&onds between atoms Molecular shapes and )"E#( theory
There is a sharp distinction between ionic and covalent bonds when the geometric
arrangements of atoms in compounds are considered. In essence, ionic bonding is
nondirectional, whereas covalent bonding is directional. That is, in ionic compounds
there is no intrinsically preferred direction in which a neighbour should lie for the
strength of bonding to be ma!imi&ed. In contrast, in a covalently bonded compound, the
atoms adopt specific locations relative to one another, as in the tetrahedral arrangement of
hydrogen atoms around the central carbon atom in methane, *:, or the angular
arrangement of atoms in 2%.
The lack of directionality of ionic bonds stems from the isotropy 1spherical symmetry2 of
the electrostatic forces between ions. #s has already been pointed out, the result of this
isotropy is that ions stack together in the locations necessary to achieve the lowest energy
and in this way give rise to the common packing patterns characteristic of many ionic
solids. When deviations from stacking schemes are observed that seem to indicate that
the ions are being held in certain orientations relative to their neighbours, it is a sign that
covalent bonding is beginning to influence the structure of the solid and that the bonding
is not purely ionic. This is the case, for e!ample, in the compound nickel arsenide 19i#s2,
which has a structure that suggests that a degree of covalent bonding is present 1)igure 7
2. It is fully apparent in the structure of diamond 1)igure V
2, in which each carbon atom is in a tetrahedral position relative to its neighbour and in
which the bonding is essentially purely covalent.
The rationali&ation of the structures adopted by purely ionic solids is essentially a
straightforward e!ercise in the analysis of electrostatic interactions between ions. The
problem of the structures of covalent compounds, both individual molecules, such as
methane, and covalently bonded solids, such as diamond, is much more subtle, for it
involves delving into the characteristics of the electron arrangements in individual atoms.
Thus, if the formation of a covalent bond is regarded as corresponding to the
accumulation of electrons in a particular region of an atom, then, to form a second bond,
electrons can be accumulated into only certain parts of the atom relative to that first
region of enhanced electron density. #s a result, the bonds will lie in a geometric array
that is characteristic of the atom. The remainder of this section focuses on this problem,
but a detailed quantum mechanical analysis is required for a full understanding of the
matter.
The theory of molecular shape known as valence/shell electron/pair repulsion 1Y(5A32
theory grew out of 0ewis4 theory, and, like that approach to bonding, Y(5A3 focuses on
the role of electron pairs. It stems from the work of the 8ritish chemists .$. Aowell and
9evil Y. (idgwick in the -=:0s and was e!tensively developed by 3.6. +illespie in
*anada and 3onald (. 9yholm in 0ondon during the -=70s. #s such, it postdates
quantum mechanical theories of bonding and shape but should be seen 1as is so common
a motivation in chemistry2 as an attempt to identify the essential features of a problem
and to formulate them into a simple qualitative procedure for rationali&ation and
prediction.
# 0ewis structure, as shown above, is a topological portrayal of bonding in a molecule. It
ascribes bonding influences to electron pairs that lie between atoms and acknowledges
the e!istence of lone pairs of electrons that do not participate directly in the bonding. The
Y(5A3 theory supposes that all electron pairs, both bonding pairs and lone pairs, repel
each other"particularly if they are close"and that the molecular shape is such as to
minimi&e these repulsions. The approach is commonly applied to species in which there
is an identifiable central atom 1the o!ygen atom in 2%, for instance2, but it is
straightforward to e!tend it to discussions of the local shape at any given atom in a
polyatomic species.
%onds between atoms )olecular shapes and V&E(* theory !pplying
V&E(* theory to simple molecules
The methane molecule, *:, can be used to illustrate the procedure for predicting
molecular shape. The 0ewis structure of this molecule ascribes four bonding electron
pairs to the carbon atom 1)igure . 2. These pairs repel one another, and
their separation is ma!imi&ed if they adopt a tetrahedral disposition around the central
carbon atom. # hydrogen atom is attached by each bonding pair, so it can be predicted
that *: is likely to be a tetrahedral species, which is in fact the case.
When applying Y(5A3 theory, attention is first focused on the electron pairs of the
central atom, disregarding the distinction between bonding pairs and lone pairs. These
pairs are then allowed to move around the central atom 1at a constant distance2 and to
take up positions that ma!imi&e their mutual separations. #s in the methane molecule,
four pairs adopt a tetrahedral disposition. The arrangements adopted by two through si!
pairs are summari&ed in the table. #t this stage, the atoms that are attached by the
bonding pairs are introduced, and the shape of the molecule is reported on the basis of the
arrangement of these atoms.
The water molecule, 2%, provides a simple e!ample. The o!ygen atom has four electron
pairs, so these pairs adopt a tetrahedral arrangement. Two of the pairs are bonding, and
hydrogen atoms are attached to them. ence, the molecule is angular. 19ote that the
shape of the molecule is determined by the disposition of the atoms, not the disposition of
the electron pairs.2 The ammonia molecule, 9;, has four electron pairs in a tetrahedral
arrangement around the nitrogen atom< three of these pairs are used to bond hydrogen
atoms, so the molecule is predicted to be trigonal pyramidal, with a lone pair in the apical
position. (ome of the names of the shapes of simple molecules are summari&ed in the
table .
The angle between electron pairs in a tetrahedral arrangement is -0=.QZ. owever,
although 2% is indeed angular and 9; is trigonal pyramidal, the angles between the
bonds are -0:Z and -0VZ, respectively. In a sense, such close agreement is quite
satisfactory for so simple an approach, but clearly there is more to e!plain. To account for
variations in bond angle, it is supposed that electron pair repulsions are greatest between
lone pairs, less between lone pairs and bonding pairs, and least between bonding pairs.
The 'ustification of this ordering has proved somewhat elusive< qualitatively it is
presumed that lone pairs, being attached only to a single centre, spread over a greater
volume than bonding pairs, which are pinned between two attracting centres. Whatever
the reason may be, the order correlates quite well with observation. Thus, in 2%, the two
lone pairs move apart a little, and the two bonding pairs move away from them by closing
the angle between one another. 0ikewise, in 9; the three bonding pairs move back from
the single lone pair to minimi&e their interaction with it. #s a result, the @9@ bond
angle decreases slightly. In each case, the predicted angle is less than the tetrahedral
angle, as is observed e!perimentally.
Y(5A3 theory is quite successful at predicting 1or, at least, rationali&ing2 the overall
shapes of molecules. Thus, the hypervalent species ()7 1sulfur he!afluoride2, with si!
bonding pairs, is predicted and found to be a regular octahedron, and A*lQ 1phosphorus
pentachloride2, with five bonding pairs, is predicted and found to be a trigonal bipyramid.
The De): 1!enon tetrafluoride2 molecule is hypervalent with si! electron pairs around the
central !enon 1De2 atom. These pairs adopt an octahedral arrangement. )our of the pairs
are bonding pairs, and two are lone pairs. #ccording to Y(5A3 theory, the repulsion
between the lone pairs is minimi&ed if they lie on opposite sides of the !enon atom,
leaving the four equatorial pairs as bonding pairs.
This analysis suggests that De): should be a planar species, which is found to be the case.
%onds between atoms )olecular shapes and V&E(* theory )olecules with
multiple bonds
There are further rules in Y(5A3 theory that simplify the discussion of species with
multiple bonds and of species in which resonance must be considered. #n analysis of the
shapes adopted by species with multiple bonds suggests that each multiple bond can be
treated as a single EsuperpairF of electrons. This rule can be 'ustified by considering the
geometric shapes that stem from two atoms sharing two or more pairs of electrons
1)igure = 2. Thus, the sulfate ion, (%:
2@
, for which a 0ewis structure is
can be treated as having the equivalent of four pairs 1two ordinary pairs and two
superpairs2 around the sulfur atom in a tetrahedral arrangement. #ll four pairs are
bonding, so the ion is predicted to be a regular tetrahedron, which it indeed is. The same
conclusion about the shape of the molecule would be drawn from another possible 0ewis
structure, in which each bond is single>
The actual molecule is a resonance hybrid of these and related structures< but, as each one
corresponds to the same geometry, no particular 0ewis structure need be selected before
one can make a prediction based on Y(5A3 theory. In other words, resonance does not
affect the shapes of molecules.
%onds between atoms )olecular shapes and V&E(* theory )olecules with
no central atom
5!amples of the manner in which Y(5A3 theory is applied to species in which there is
no central atom are provided by ethane 1*272, ethylene 1*2:2, and acetylene 1*222, the
0ewis structures for which are, respectively, the following>

In each case, consider the local environment of each carbon atom. In ethane there are four
bonding pairs around each carbon atom, so every carbon atom is linked to its four
neighbours 1one carbon atom and three hydrogen atoms2 by a tetrahedral array of bonds.
The bond angles in ethane are indeed all close to -0=Z. In ethylene each carbon atom
possesses two ordinary bonding pairs 1linking it to hydrogen atoms2 and one superpair
1linking it to the other carbon atom2. These three pairs, and the corresponding bonds,
adopt a planar triangular arrangement, and the @*@ and @*G* angles are predicted
to be close to -20Z, as is found e!perimentally. It is less apparent from this analysis, but
understandable once it is reali&ed that the superpair is actually two shared pairs 1)igure
=2, that the ethylene molecule is predicted to be planar. 5ach carbon atom in an acetylene
molecule has one bonding pair 1to hydrogen2 and one superpair 1to the other carbon
atom2. The molecule is therefore e!pected to be linear, as is found in practice. The
linearity of the molecule can be appreciated by referring to )igure =.
%onds between atoms )olecular shapes and V&E(* theory $imitations of
the V&E(* model
The Y(5A3 theory is simple yet powerful. 9evertheless, like any simplified model, it has
its limitations. )irst, although it predicts that the bond angle in 2% is less than the
tetrahedral angle, it does not make any attempt to predict the magnitude of the decrease.
(econd, the theory makes no predictions about the lengths of the bonds, which is another
aspect of the shape of a molecule. Third, it ascribes the entire criterion of shape to
electrostatic repulsions between bonding pairs, when in fact there are numerous
contributions to the total energy of a molecule, and electrostatic effects are not
necessarily the dominant ones. )ourth, the theory relies on some vague concepts, such as
the difference in repelling effects of lone pairs and bonding pairs. There also are some
species for which Y(5A3 theory fails. 9evertheless, despite these limitations and
uncertainties, Y(5A3 theory is a useful rule of thumb and can be used with reasonable
confidence for numerous species.
&onds between atoms The polarity of molecules
There are three main properties of chemical bonds that must be considered"namely,
their strength, length, and polarity. The polarity of a bond is the distribution of electrical
charge over the atoms 'oined by the bond. (pecifically, it is found that, while bonds
between identical atoms 1as in 22 are electrically uniform in the sense that both
hydrogen atoms are electrically neutral, bonds between atoms of different elements are
electrically inequivalent. In hydrogen chloride, for e!ample, the hydrogen atom is slightly
positively charged whereas the chlorine atom is slightly negatively charged. The slight
electrical charges on dissimilar atoms are called partial charges, and the presence of
partial charges signifies the occurrence of a polar bond.
The polarity of a bond arises from the relative electronegativities of the elements.
5lectronegativity, it will be recalled, is the power of an atom of an element to attract
electrons toward itself when it is part of a compound. Thus, although a bond in a
compound may consist of a shared pair of electrons, the atom of the more electronegative
element will draw the shared pair toward itself and thereby acquire a partial negative
charge. The atom that has lost its equal share in the bonding electron pair acquires a
partial positive charge because its nuclear charge is no longer fully canceled by its
electrons.
The e!istence of equal but opposite partial charges on the atoms at each end of a
heteronuclear bond 1i.e., a bond between atoms of different elements2 gives rise to an
electric dipole. The magnitude of this dipole is e!pressed by the value of its dipole
moment, [, which is defined as the product of the magnitude of the partial charges times
their separation 1essentially, the length of the bond2. The dipole moment of a
heteronuclear bond can be estimated from the electronegativities of the atoms # and 8, R#
and R8, respectively, by using the simple relation
where , denotes the unit debye, which is used for reporting molecular dipole moments 1-
, G ;.;: U -0
@;0
coulombTmetre2. $oreover, the negative end of the dipole lies on the
more electronegative atom. If the two bonded atoms are identical, it follows that the
dipole moment is &ero and the bond is nonpolar.
#s the difference in electronegativity between two covalently bonded atoms increases,
the dipolar character of the bond increases as the partial charges increase. When the
electronegativities of the atoms are very different, the attraction of the more
electronegative atom for the shared electron pair is so great that it effectively e!ercises
complete control over them. That is, it has gained possession of the pair, and the bond is
best regarded as ionic. Ionic and covalent bonding therefore can be regarded as
constituting a continuum rather than as alternatives. This continuum can be e!pressed in
terms of resonance by regarding a bond between atoms # and 8 as a resonance between a
purely covalent form, in which the electrons are shared equally, and a purely ionic form,
in which the more electronegative atom 182 has total control over the electrons>
#s the electronegativity difference increases, the resonance lies increasingly in favour of
the ionic contribution. When the electronegativity difference is very large, as between an
electropositive atom like sodium and an electronegative atom like fluorine, the ionic
structure dominates the resonance, and the bonding can be regarded as ionic. Thus, as the
electronegativity difference of the two bonded elements increases, a nonpolar bond gives
way to a polar bond, which in turn becomes an ionic bond. There are, in fact, no purely
ionic bonds, 'ust as there are no purely covalent bonds< bonding is a continuum of types.
5ven a homonuclear bond, which is a bond between atoms of the same element 1as in
*l22, is not purely covalent, because a more accurate description would be in terms of
ionic/covalent resonance>
That the species is nonpolar despite the occurrence of ionic contributions stems from the
equal contributions of the ionic structures *l
@
*l
?
and *l
?
*l
@
and their canceling dipoles.
That *l2 is commonly regarded as a covalently bonded species stems from the dominant
contribution of the structure *l@*l to this resonance mi!ture. In contrast, the valence
bond theory wavefunction 1see below The quantum mechanics of bonding> Yalence bond
theory2 of hydrogen chloride would be e!pressed as the resonance hybrid
In this case, the two ionic structures would contribute different amounts 1because the
elements have different electronegativities2, and the larger contribution of
?
*l
@
is
responsible for the presence of partial charges on the atoms and the polarity of the
molecule.
# polyatomic molecule will have polar bonds if its atoms are not identical. owever,
whether or not the molecule as a whole is polar 1i.e., has a non&ero electric dipole
moment2 depends on the shape of the molecule. )or e!ample, the carbon/o!ygen bonds
in carbon dio!ide are both polar, with the partial positive charge on the carbon atom and
the partial negative charge on the more electronegative o!ygen atom. The molecule as a
whole is nonpolar, however, because the dipole moment of one carbon/o!ygen bond
cancels the dipole moment of the other, for the two bond dipole moments point in
opposite directions in this linear molecule. In contrast, the water molecule is polar. 5ach
o!ygen/hydrogen bond is polar, with the o!ygen atom bearing the partial negative charge
and the hydrogen atom the partial positive charge. 8ecause the molecule is angular rather
than linear, the bond dipole moments do not cancel, and the molecule has a non&ero
dipole moment.
The polarity of 2% is of profound importance for the properties of water. It is partly
responsible for the e!istence of water as a liquid at room temperature and for the ability
of water to act as a solvent for many ionic compounds. The latter ability stems from the
fact that the partial negative charge on the o!ygen atom can emulate the negative charge
of anions that surround each cation in the solid and thus help minimi&e the energy
difference when the crystal dissolves. The partial positive charge on the hydrogen atoms
can likewise emulate that of the cations surrounding the anions in the solid.
The quantum mechanics of bonding
The preceding discussion has outlined the general approach to covalent bonding and has
shown how it is still widely employed for a qualitative understanding of molecules. It is
incomplete in many respects, however. )irst, the role of the electron pair remains
une!plained but appears to be the hinge of both 0ewis4 theory and the Y(5A3 theory.
(econd, there is evidence that suggests that 0ewis4 theory overemphasi&es the role of
electron pairs. $ore fundamentally, little has been said about the distribution of bonding
electrons in terms of orbitals, although it has been shown that in atoms the distributions
of electrons are described by wavefunctions. )inally, the models that have been described
have little quantitative content> they do not lead to bond lengths or precise bond angles,
nor do they give much information about the strengths of bonds.
# full theory of the chemical bond needs to return to the roots of the behaviour of
electrons in molecules. That is, the role of the electron pair and the quantitative
description of bonding must be based on the (chrHdinger equation and the Aauli
e!clusion principle. This section describes the general features of such an approach. %nce
again, the discussion will be largely qualitative and conceptual rather than mathematical
and numerical. owever, the character of the presentation here should not be taken to
imply that the current understanding of molecules is not rigorous, quantitative, and
precise.
(everal difficulties are encountered at the outset of the application of the (chrHdinger
equation to molecules. 5ven the simplest molecules consist of two nuclei and several
electrons, and interesting molecules may contain a thousand atoms and tens of thousands
of electrons. (o that any progress of a generally applicable kind can be made,
appro!imations are necessary.
%ne appro!imation is common to all discussions of molecules. The 8orn/%ppenheimer
appro!imation, which was introduced by $a! 8orn and 6. 3obert %ppenheimer in -=2V,
separates the motion of the electrons in a molecule from the motion of the nuclei. The
separation is based on the fact that the nuclei are much heavier than the electrons and
move more slowly. ence, even though nuclei do move, the electrons can respond to
their new positions almost instantaneously. That being the case, it is permissible to
consider the nuclei as stationary in a given arrangement and then to solve the (chrHdinger
equation for the electrons in that stationary framework of nuclei. In order to e!plore how
the energy of the molecule changes as the nuclei change their positions, a series of static
nuclear arrangements can be selected, and the (chrHdinger equation solved for the
electrons in each stationary arrangement.
The data obtained from such a procedure can be used to construct a molecular potential
energy curve, a graph that shows how the energy of the molecule varies as bond lengths
and bond angles are changed. # typical curve for a diatomic molecule, in which only the
internuclear distance is variable, is shown in )igure -0 . The energy
minimum of this curve corresponds to the observed bond length of the molecule. The
depth of the minimum is 1apart from a small correction for the vibrational properties of
the bond2 equal to the bond dissociation energy and hence indicates the tightness with
which the two atoms are held together. The steepness of the walls of the curve, which
shows how rapidly the energy changes as the nuclear separation changes, indicates the
rigidity of the bond. Thus, quantitative information can be obtained from such an
approach.
5ven the 8orn/%ppenheimer appro!imation is only one of the appro!imations needed for
the study of the molecule. It separates out the nuclear motion and leaves untouched the
need to solve the (chrHdinger equation for several 1and perhaps tens of thousands2 of
electrons. Two ma'or alternative appro!imations beyond the 8orn/%ppenheimer approach
have been devised to tackle this aspect of the problem. The first to be proposed 1by
Walter eitler and )rit& 0ondon in -=2V and substantially developed by 6ohn (later and
0inus Aauling in the -=;0s2 is valence bond 1Y82 theory. This theory introduced
language into chemistry that is still widely used, particularly in the discussion of organic
compounds, but it has been somewhat overshadowed in quantitative investigations by its
rival. The latter, molecular orbital 1$%2 theory, was introduced in -=2V by 3obert (.
$ulliken and )riedrich und. It has undergone considerable development and is the
principal model for the calculation of molecular properties and for general discussions of
compounds.
The quantum mechanics of bonding )alence bond theory
The basis of Y8 theory is the 0ewis concept of the electron/pair bond. 8roadly speaking,
in Y8 theory a bond between atoms # and 8 is formed when two atomic orbitals, one
from each atom, merge with one another 1the technical term is overlap2, and the electrons
they contain pair up 1so that their spins are LK2. The merging of orbitals gives rise to
constructive interference"i.e., an enhancement of amplitude"between the
wavefunctions in the areas where they overlap, and hence an enhanced amplitude results
in the internuclear region. #s a consequence of the formation of this region of heightened
amplitude, there is an increased probability of finding he electrons in the internuclear
region 1so echoing 0ewis4 conception of the bond2 and, by implication, a lowering of the
energy of the molecule.
The Y8 theory can be put in the broader conte!t of quantum mechanics by drawing on
the superposition principle and the Aauli e!clusion principle 1see quantum mechanics2.
The two principles establish more precisely the type of orbital merging that is required
and also show that, to achieve that merging, the two electrons must pair their spins. The
technical 'ustification will not be presented here.
The quantum mechanics of bonding Valence bond theory Formation of +
and , bonds
#s an illustration of the Y8 procedure, consider the structure of 2%. )irst, note that the
valence/shell electron configuration of an o!ygen atom is 2s
2
2px
2
2py
-
2pz
-
, with an
unpaired electron in each of two 2p orbitals, and
is the 0ewis diagram for the atom. 5ach hydrogen atom has an unpaired -s electron 1T2
that can pair with one of the unpaired o!ygen 2p electrons. ence, a bond can form by
the pairing of each hydrogen electron with an o!ygen electron and the overlap of the
orbitals they occupy. The electron distribution arising from each overlap is cylindrically
symmetrical around the respective %@ a!is and is called a \ bond. The Y8 description
of 2% is therefore that each hydrogen atom is linked to the o!ygen atom by a \ bond
formed by pairing of a hydrogen -s electron and an o!ygen 2p electron. 8ecause a
wavefunction can be written for this structure, an energy can be calculated by solving the
(chrHdinger equation, and a bond length can be determined by varying the nuclear
separation and identifying the separation that results in the minimum energy.
The term \ bond is widely used in chemistry to denote an electron distribution like that in
an o!ygen/hydrogen bond, specifically one that has cylindrical symmetry about the line
between the two bonded atoms. It is not the only type of bond, however, as can be
appreciated by considering the structure of a nitrogen molecule, 92. 5ach nitrogen atom
has the valence/shell electron configuration 2s
2
2px
-
2py
-
2pz
-
. If the z direction is taken to
lie along the internuclear a!is of the molecule, then the electrons in the two 2pz orbitals
can pair and overlap to form a \ bond. owever, the 2px orbitals now lie in the wrong
orientation for head/to/head overlap, and they overlap side/to/side instead. The resulting
electron distribution is called a ] bond. # ] bond also helps to hold the two atoms
together, but, because the region of ma!imum electron density produced by the overlap is
off the line of the internuclear a!is, it does not do so with the same strength as a \ bond.
The 2py electrons can pair and overlap in the same way and give rise to a second ] bond.
Therefore, the structure of an 92 molecule consists of one \ bond and two ] bonds. 9ote
how this corresponds to and refines the 0ewis description of the >9X9> molecule.
In summary, a single bond in a 0ewis structure corresponds to a \ bond of Y8 theory. #
double bond corresponds to a \ bond plus a ] bond, and a triple bond corresponds to a \
bond plus two ] bonds.
The quantum mechanics of bonding Valence bond theory (romotion of
electrons
Yalence bond theory runs into an apparent difficulty with *:. The valence/shell electron
configuration of carbon is 2s
2
2px
-
2py
-
, which suggests that it can form only two bonds to
hydrogen atoms, in which case carbon would have a valence of 2. The normal valence of
carbon is :, however. This difficulty is resolved by noting that only the overall energy of
a molecule is important, and, as long as a process leads to a lowering of energy, it can
contribute even if an initial investment of energy is required. In this case, Y8 theory
allows promotion to occur, in which an electron is elevated to a higher orbital. Thus, a
carbon atom is envisaged as undergoing promotion to the valence configuration
2s
-
2px
-
2py
-
2pz
-
as a *: molecule is formed. #lthough promotion requires energy, it
enables the formation of four bonds, and overall there is a lowering of energy. *arbon is
particularly suited to this promotion because the energy involved is not very great< hence
the formation of tetravalent carbon compounds is the rule rather than the e!ception.
The quantum mechanics of bonding Valence bond theory Hybridi-ation
The discussion is not yet complete, however. If this description of carbon were taken at
face value, it would appear that, whereas three of the * bonds in methane are formed
from carbon 2p orbitals, one is formed from a carbon 2s orbital. It is well established
e!perimentally, however, that all four bonds in methane are identical.
Suantum mechanical considerations resolve this dilemma by invoking hybridi&ation.
ybridi&ation is the mi!ing of atomic orbitals on the same atom. When the 2s and three
2p orbitals of a carbon atom are hybridi&ed, they give rise to four lobelike sp
;
hybrid
orbitals that are equivalent to one another apart from their orientations, which are toward
the four corners of a regular tetrahedron. 5ach hybrid orbital contains an unpaired
electron and can form a \ bond by pairing with a -s electron of a hydrogen atom. ence,
the Y8 structure of methane is described as consisting of four equivalent \ bonds formed
by overlap of the s orbitals of the hydrogen atoms with sp
;
hybrid orbitals of the carbon
atom.
ybridi&ation is a ma'or contribution of Y8 theory to the language of chemistry. The
structure of ethylene can be e!amined in Y8 terms to illustrate the use of hybridi&ation.
To reproduce the 0ewis structure given earlier, it is necessary to contrive a double bond
1i.e., a \ bond plus a ] bond2 between the two carbon atoms. (uch a bonding pattern can
be achieved by selecting the carbon 2s orbital, from which an electron has been
promoted, and two of its 2p orbitals for hybridi&ation, leaving one 2p orbital
unhybridi&ed and ready for forming a ] bond. When one 2s and two 2p orbitals are
hybridi&ed, they form sp
2
hybrid orbitals, which have lobelike boundary surfaces that
point to the corners of an equilateral triangle< the unhybridi&ed 2p orbital lies
perpendicular to the plane of the triangle 1)igure -- 2. 5ach of the orbitals
contains a single electron. Two of the hybrids can form \ bonds to two hydrogen atoms,
and one of the hybrids can form a \ bond to the other carbon atom 1which has undergone
similar hybridi&ation2. The unhybridi&ed 2p orbitals are now side/by/side and can overlap
to form a ] bond.
This description conforms to the 0ewis description. It also e!plains naturally why
ethylene is a planar molecule, because twisting one end of the molecule relative to the
other reduces the overlap between the 2p orbitals and hence weakens the ] bond. #ll
double bonds confer a torsional rigidity 1a resistance to twisting2 to the parts of molecules
where they lie.
The quantum mechanics of bonding Valence bond theory *esonant
structures
The description of the planar he!agonal ben&ene molecule, *77, illustrates another
aspect of Y8 theory. 5ach of the si! carbon atoms is taken to be sp
2
hybridi&ed. Two of
the hybrid orbitals are used to form \ bonds with the carbon atom neighbours, and one is
used to form a \ bond with a hydrogen atom. The unhybridi&ed carbon 2p orbitals are in
a position to overlap and form ] bonds with their neighbours 1)igure -2 2.
owever, there are several possibilities for pairing< two are as follows>
There is a Y8 wavefunction for each of these so/called Cekul^ structures. 1They are so
called after )riedrich #ugust Cekul^, who is commonly credited with having first
proposed the he!agonal structure for ben&ene in -.7Q< however, a cyclic structure had
already been proposed by 6oseph 0oschmidt four years earlier.2 The actual structure is a
superposition 1sum2 of the two wavefunctions> in Y8 terms, the structure of ben&ene is a
resonance hybrid of the two canonical structures. In quantum mechanical terms, the
blending effect of resonance in the 0ewis approach to bonding is the superposition of
wavefunctions for each contributing canonical structure. The effect of resonance is the
sharing of the double/bond character around the ring, so that each carbon/carbon bond
has a mi!ed single/ and double/bond character. 3esonance also 1for quantum mechanical
reasons2 lowers the energy of the molecule relative to either contributing canonical
structure. Indeed, ben&ene is a molecule that is surprisingly resistant to chemical attack
1double bonds, rather than being a source of molecular strength and stability, are usually
the targets of chemical attack2 and is more stable than its structure suggests.
%ne of the difficulties that has rendered Y8 computationally unattractive is the large
number of canonical structures, both covalent and ionic, that must be used in order to
achieve quantitatively reliable results< in some cases tens of thousands of structures must
be employed. 9evertheless, Y8 theory has influenced the language of chemistry
profoundly, and the concepts of \ and ] bonds, hybridi&ation, and resonance are a part of
the everyday vocabulary of the sub'ect.
The quantum mechanics of bonding Molecular orbital theory
The alternative quantum mechanical theory of the electronic structures of molecules is
$% theory. This approach was introduced about the same time as Y8 theory but has
proved more amenable to quantitative implementation on computers. It is now virtually
the only technique employed in the computational investigation of molecules. 0ike Y8
theory, it has introduced a language that is widely used in chemistry, and many chemists
discuss chemical bonds in terms that combine both theories.
6ust as an atomic orbital is a wavefunction that describes the distribution of an electron
around the nucleus of an atom, so a molecular orbital 1an $%2 is a wavefunction that
describes the distribution of an electron over all the nuclei of a molecule. If the amplitude
of the $% wavefunction is large in the vicinity of a particular atom, then the electron has
a high probability of being found there. If the $% wavefunction is &ero in a particular
region, then the electron will not be found there.
#lthough an $% can in principle be determined by solving the (chrHdinger equation for
an electron in the electrostatic field of an array of nuclei, in practice an appro!imation is
always adopted. In this appro!imation, which is known as the linear combination of
atomic orbitals 10*#%2 appro!imation, each $% is constructed from a superposition of
atomic orbitals belonging to the atoms in the molecule. The si&e of the contribution of an
orbital from a particular atom indicates the probability that the electron will be found on
that atom. The actual shape of the molecular orbital 1and indirectly its energy2 is a
reflection of the e!tent to which the individual atomic orbitals interfere with one another
either constructively or destructively.
The quantum mechanics of bonding )olecular orbital theory )olecular
orbitals of H
.
and He
.

The procedure can be introduced by considering the 2 molecule. Its molecular orbitals
are constructed from the valence/shell orbitals of each hydrogen atom, which are the -s
orbitals of the atoms. Two superpositions of these two orbitals can be formed, one by
summing the orbitals and the other by taking their difference. In the former, the
amplitudes of the two atomic orbitals interfere constructively with one another, and there
is consequently an enhanced amplitude between the two nuclei. #s a result, any electron
that occupies this molecular orbital has a high probability of being found between the two
nuclei, and its energy is lower than when it is confined to either atomic orbital alone. This
combination of atomic orbitals is therefore called a bonding orbital. $oreover, because it
has cylindrical symmetry about the internuclear a!is, it is designated a \ orbital and
labeled -\.
The $% formed by taking the difference of the two -s orbitals also has cylindrical
symmetry and hence is also a \ orbital. Taking the difference of the two atomic orbitals,
however, results in destructive interference in the internuclear region where the amplitude
of one orbital is subtracted from the other. This destructive interference is complete on a
plane midway between the nuclei, and hence there is a nodal plane"i.e., a plane of &ero
amplitude"between the nuclei. #ny electron that occupies this orbital is e!cluded from
the internuclear region, and its energy is higher than it would be if it occupied either
atomic orbital. The orbital arising in this way is therefore called an antibonding orbital< it
is often denoted \_ 1and referred to as Esigma starF2 or, because it is the second of the
two \ orbitals, 2\.
The molecular orbital energy/level diagram, which is a diagram that shows the relative
energies of molecular orbitals, for the 2 molecule is shown in )igure -; .
%n either side of the central ladder are shown the energies of the -s orbitals of atoms #
and 8, and the central two/rung ladder shows the energies of the bonding and antibonding
combinations. %nly at this stage, after setting up the energy/level diagram, are the
electrons introduced. In accord with the Aauli e!clusion principle, at most two electrons
can occupy any one orbital. In 2 there are two electrons, and, following the building/up
principle, they enter and fill the lower/energy bonding combination. ence the electron
configuration of the molecule is denoted -\
2
, and the stability of the molecule stems from
the occupation of the bonding combination. Its low energy results in turn 1in the
conventional interpretation, at least2 from the accumulation of electron density in the
internuclear region because of constructive interference between the contributing atomic
orbitals.
The central importance of the electron pair for bonding arises naturally in $% theory via
the Aauli e!clusion principle. # single electron pair is the ma!imum number that can
occupy a bonding orbital and hence give the greatest lowering of energy. owever, $%
theory goes beyond 0ewis4 approach by not ascribing bonding to electron pairing< some
lowering of energy is also achieved if only one electron occupies a bonding orbital, and
so the fact that 2
?
e!ists 1with the electron configuration -\
-
2 is no longer pu&&ling.
The molecular orbital energy/level diagram shown in )igure -; also applies 1with
changes of detail in the energies of the molecular orbitals2 to the hypothetical species
e2. owever, this species has four valence electrons, and its configuration would be
-\
2
2\
2
. #lthough there is a bonding influence from the two bonding electrons, there is an
antibonding influence from two antibonding electrons. #s a result, the e2 molecule does
not have a lower energy than two widely separated helium atoms and hence has no
tendency to form. 1The overall effect is in fact slightly antibonding.2 The role of the noble
gas configuration now can be seen from a different perspective> the electrons that are
provided by each closed/shell atom fill both the bonding and antibonding orbitals, and
they result in no net lowering of energy< in fact, they give rise to an increase in energy
relative to the separated atoms.
The molecular orbitals of other species are constructed in an analogous way. In general,
the orbitals in the valence shells of each atom are considered first 1not, initially, the
electrons those orbitals contain2. Then the sets of these orbitals that have the same
symmetry with respect to the internuclear a!is are selected. 1This point is illustrated
below.2 8onding and antibonding combinations of each set are then formed, and from n
atomic orbitals n such molecular orbitals are formed. The molecular orbital energy/ level
diagram that results is constructed by putting the molecular orbitals in order of increasing
number of internuclear nodal planes, the orbital with no such nodal plane lying at lowest
energy and the orbital with nodal planes between all the atoms lying at highest energy. #t
this stage, the valence electrons provided by the atoms are allowed to occupy the
available orbitals in accord with the general rules of the building/up principle, with no
more than two electrons in each orbital and in accord with und4s rule if more than one
orbital is available for occupation.
The quantum mechanics of bonding )olecular orbital theory )olecular
orbitals of period'. diatomic molecules
#s a first illustration of this procedure, consider the structures of the diatomic molecules
formed by the period/2 elements 1such as 92 and %22. 5ach valence shell has one 2s and
three 2p orbitals, and so there are eight atomic orbitals in all and hence eight molecular
orbitals that can be formed. The energies of these atomic orbitals are shown on either side
of the molecular orbital energy/level diagram in )igure -: . 1It may be
recalled from the discussion of atoms that the 2p orbitals have higher energy than the 2s
orbitals.2 If the z a!is is identified with the internuclear a!is, the 2s and 2pz orbitals on
each atom all have cylindrical symmetry around the a!is and hence may be combined to
give \ orbitals. There are four such atomic orbitals, so four \ orbitals can be formed.
These four molecular orbitals lie typically at the energies shown in the middle of )igure
-:. The 2px orbitals on each atom do not have cylindrical symmetry around the
internuclear a!is. They overlap to form bonding and antibonding ] orbitals. 1The name
and shape reflects the ] bonds of Y8 theory.2 The same is true of the 2py orbitals on each
atom, which form a similar pair of bonding and antibonding ] orbitals whose energies are
identical to those of bonding and antibonding ] orbitals, respectively, formed from the
2px orbitals. The precise locations of the ] orbitals relative to those of the \ orbitals
depend on the species> for simplicity here they will be taken to be as shown in )igure -:.
9ow consider the structure of 92. There are 2 U Q G -0 valence electrons to
accommodate. These electrons occupy the five lowest/energy $%s and hence result in
the configuration -\
2
2\
2
-]
:
;\
2
. 9ote that only the orbitals in the lower portion of the
diagram of )igure -: are occupied. This configuration accounts for the considerable
strength of the bonding in 92 and consequently its ability to act as a diluent for the
o!ygen in the atmosphere, because the %2 molecules are much more likely to react than
the 92 molecules upon collision with other molecules. #n analysis of the identities of the
orbitals shows, after allowing for the cancellation of bonding effects by antibonding
effects, that the form of the electron configuration is 1\ bonding orbital2
2
1] bonding
orbitals2
:
. If each doubly occupied \ orbital is identified with a \ bond and each doubly
occupied ] orbital with a ] bond, then the structure obtained by this $% procedure
matches both the Y8 description of the molecule and the >9X9> 0ewis description.
To see how the $% approach transcends the 0ewis approach 1and, in this instance, the
Y8 approach as well2, consider the electronic configuration of %2. The same $% energy/
level diagram 1with changes of detail2 can be used because the o!ygen atoms provide the
same set of atomic orbitals. 9ow, however, there are 2 U 7 G -2 valence orbitals to
accommodate. The first -0 electrons reproduce the configuration of 92. The last two enter
the 2]_ antibonding orbital, thereby reducing the net configuration to one \ bond and one
] bond. That is, %2 is a doubly/bonded species, in accord with the 0ewis structure %G%.
owever, because there are two 2] orbitals and only two electrons to occupy them, the
two electrons occupy different orbitals with parallel spins 1recall und4s rule2. Therefore,
the magnetic fields produced by the two electrons do not cancel, and %2 is predicted to be
a paramagnetic species. That is in fact the case. (uch a property was completely outside
the competence of 0ewis4 theory to predict and must be contrived in Y8 theory. It was an
early ma'or triumph of $% theory.
The quantum mechanics of bonding )olecular orbital theory )olecular
orbitals of polyatomic species
The principal qualitative difference between $% theory and Y8 theory becomes obvious
when the ob'ects of study are polyatomic, rather than diatomic, species. The ben&ene
molecule is considered again but in this case from the viewpoint of its molecular orbitals.
The atomic orbitals that provide the so/called basis set for the molecular orbitals 1i.e., the
ones from which the $%s are constructed2 are the carbon 2s and 2p orbitals and the
hydrogen -s orbitals. #ll these orbitals e!cept one 2p orbital on each carbon atom lie in
the plane of the molecule, so they naturally form two sets that are distinguished by their
symmetries. This discussion concentrates on the molecular orbitals that are constructed
from the si! perpendicular 2p orbitals, which form the ] orbitals of the molecule< the
remaining orbitals form a framework of \ orbitals.
(i! molecular orbitals, which are labeled -a, -e, 2e, and 2a, as shown in )igure -Q
, can be built from these si! 2p orbitals. The two -e orbitals and the two
2e orbitals each have the same energy. The si! molecular orbitals are various sums and
differences of the si! 2p orbitals, and they differ in the number and position of their
internuclear nodal planes 1i.e., areas of low electron density2. #s before, the greater the
number of these nodal planes, the more the electrons that occupy the orbitals are
e!cluded from the region between the nuclei, and hence the higher the energy. The
resulting molecular orbital energy/level diagram is shown alongside the orbitals in the
illustration. The lowest/energy -a orbital has no nodal plane, so there is ma!imum
positive overlap. The two degenerate -e orbitals each have one nodal plane, the
degenerate 2e orbitals have two nodal planes each, and the high/energy 2a orbital has
three nodal planes. The crucial difference from the cases considered earlier is that the
molecular orbitals spread over more than two atoms. That is, they are delocali&ed
orbitals, and electrons that occupy them are delocali&ed over several atoms 1here, as
many as si! atoms, as in the -a orbital2.
5ach carbon atom supplies one electron to the ] system 1the other 2: valence electrons
have occupied the -2 low/energy \ orbitals that are not directly of interest here2. These
si! electrons occupy the three lowest/energy molecular orbitals. 9otice that none of the
net antibonding orbitals is occupied< this is a part of the e!planation of the considerable
stability of the ben&ene molecule.
The quantum mechanics of bonding )olecular orbital theory The role of
delocali-ation
In the Y8 description of the ben&ene molecule, each double bond is locali&ed between a
particular pair of atoms, but resonance spreads that character around the ring. In $%
theory, there are three occupied ] orbitals, and hence three contributions to double/bond
character, but each electron pair is spread around the ring and helps to draw either all the
atoms together 1the -a orbital2 or several of the atoms together 1the two -e orbitals2.
Thus, delocali&ation distributes the bonding effect of an electron pair over the atoms of
the molecule, and hence one electron pair can contribute to the bonding of more than two
atoms.
(everal problems that remained unsolved in the earlier discussion of 0ewis structures can
be unraveled. It has already been shown that one electron can contribute to bonding if it
occupies a bonding orbital< therefore the problem of the e!istence of one/electron species
is resolved.
ypervalence is taken care of, without having to invoke octet e!pansion, by the
distributed bonding effect of delocali&ed electrons. *onsider ()7, which according to
0ewis4 theory needs to use two of its ;d orbitals in addition to its four ;s and ;p orbitals
to accommodate si! pairs of bonding electrons. In $% theory, the four ;s and ;p orbitals
of sulfur and one 2p orbital of each fluorine atom are used to build - ? ; ? 7 G -0
molecular orbitals. These -0 $%s are delocali&ed to varying degrees over the seven
atoms of the molecule. alf of them have a net bonding character and half of them a net
antibonding character between the sulfur and fluorine atoms. There are 7 sulfur valence
electrons to accommodate and 7 U - G 7 fluorine electrons for a total of -2. The first -0 of
these electrons occupy the net bonding orbitals< the remaining two occupy the lowest/
energy antibonding orbital. In fact, this orbital is so weakly antibonding that it is best to
regard it as nonbonding and as having little effect on the stability of the molecule. In any
event, its weakly antibonding character is distributed over all si! fluorine atoms, 'ust as
the other five pairs of electrons help to bind all si! fluorine atoms to the central sulfur
atom. The net effect of the -2 electrons is therefore bonding, and delocali&ation
eliminates the need to invoke any role for d orbitals. The quantitative description of the
forms and energies of the molecular orbitals is improved by the inclusion of ;d orbitals in
the basis set, but only a small admi!ture is needed. There is certainly no need to invoke
;d orbitals as a necessary component of the description of bonding and no need to regard
this hypervalent molecule as an e!ample of a species with an e!panded octet. %ctet
e!pansion is a rule of thumb, a correlation of an observation with the presence of
available d orbitals, and not a valid e!planation.
The other remaining outstanding problem is that of electron/deficient compounds, as
typified by 827. (uch molecules are classified as electron deficient because, in 0ewis
terms, there are fewer than two electrons available per bond. owever, a consequence of
delocali&ation is that the bonding influence of an electron pair is distributed over all the
atoms in a molecule. ence, it is easy to construct molecular orbitals that can achieve the
binding of eight atoms by si! electron pairs. The question to consider is not why electron/
deficient compounds e!ist but why they are so rare. The answer lies in the smallness of
the boron and hydrogen atoms, which allows them to get so close to one another that the
cluster can be held together efficiently by a few delocali&ed pairs of electrons. 0ewis was
fortunate because the rules he adduced were generally applicable to larger atoms< there
are more large atoms in the periodic table than there are atoms that are small enough for
electron pair delocali&ation to be a dominant feature of their structures.
The quantum mechanics of bonding )olecular orbital theory #omparison
of the V% and )/ theories
The language that molecular orbital theory brings to chemistry is that of bonding and
antibonding orbitals and delocali&ation of electrons. The theory is presented here as an
alternative to valence bond theory, and the formulation of the theory is quite different.
owever, both theories involve appro!imations to the actual electronic structures of
molecules, and both can be improved. Yalence bond theory is improved by incorporating
e!tensive ionic/covalent resonance< molecular orbital theory is enhanced by allowing for
a variety of occupation schemes for molecular orbitals 1the procedure of configuration
interaction2. #s these two improvement schemes are pursued, the wavefunctions
generated by the two approaches converge on one another and the electron distributions
they predict become identical.
Yalence bond theory is widely used when the molecular property of interest is identifiable
with the properties of individual bonds. It is therefore commonly employed in organic
chemistry, where the reactions of molecules are often discussed in terms of the properties
of their functional groups. The latter are small locali&ed regions of a molecule 1such as a
double bond2 or particular clusters of atoms 1such as an % group2. $olecular orbital
theory is widely used to describe properties that are most naturally discussed in terms of
delocali&ation. (uch properties include the spectroscopic properties of molecules, in
which electromagnetic radiation is used to e!cite an electron from one molecular orbital
to another and all the atoms contribute to the shift in electron density that accompanies
the e!citation.
Intermolecular forces
$olecules cohere even though their ability to form chemical bonds has been satisfied.
The evidence for the e!istence of these weak intermolecular forces is the fact that gases
can be liquefied, that ordinary liquids e!ist and need a considerable input of energy for
vapori&ation to a gas of independent molecules, and that many molecular compounds
occur as solids. The role of weak intermolecular forces in the properties of gases was first
e!amined theoretically by the ,utch scientist 6ohannes van der Waals, and the term van
der Waals forces is used synonymously with intermolecular forces. Bnder certain
conditions, weakly bonded clusters of molecules 1such as an argon atom in association
with a hydrogen chloride molecule2 can e!ist< such delicately bonded species are called
van der Waals molecules.
There are many types of intermolecular forces< the repulsive force and four varieties of
attractive force are discussed here. In general, the energy of interaction varies with
distance, as shown by the graph in )igure -7 . #ttractive forces dominate
to the distance at which the two molecules come into contact, then strong repulsive forces
come into play and the potential energy of two molecules rises abruptly. The shape of the
intermolecular potential energy curve shown in the illustration resembles that of the
molecular potential energy curve in )igure -0. The minimum of the former is much
shallower, however, showing that forces between molecules are typically much weaker
than the forces responsible for chemical bonds within molecules.
Intermolecular forces (epulsive force
The repulsive part of the intermolecular potential is essentially a manifestation of the
overlap of the wavefunctions of the two species in con'unction with the Aauli e!clusion
principle. It reflects the impossibility for electrons with the same spin to occupy the same
region of space. $ore rigorously, the steep rise in energy is illustrated by the behaviour of
two helium atoms and their possession of the configuration -\
2
2\
2
1see above )igure -;2.
The antibonding effect of the upper energy orbital dominates the bonding effect of the -\
orbital at all separations, and the energy of the former rises more rapidly than that of the
latter falls. *onsequently, as the internuclear separation is decreased, the total energy
rises steeply. #ll closed/shell species behave in a similar manner for much the same
reason.
Intermolecular forces *ipole+dipole interaction
The first of the four bonding interactions discussed here is the dipole`dipole interaction
between polar molecules. It will be recalled that a polar molecule has an electric dipole
moment by virtue of the e!istence of partial charges on its atoms. %pposite partial
charges attract one another, and, if two polar molecules are orientated so that the opposite
partial charges on the molecules are closer together than their like charges, then there will
be a net attraction between the two molecules. This type of intermolecular force
contributes to the condensation of hydrogen chloride to a liquid at low temperatures. The
dipole`dipole interaction also contributes to the weak interaction between molecules in
gases, because, although molecules rotate, they tend to linger in relative orientations in
which they have low energy"namely, the mutual orientation with opposite partial
charges close to one another.
Intermolecular forces *ipole+induceddipole interaction
The second type of attractive interaction, the dipole`induced/dipole interaction, also
depends on the presence of a polar molecule. The second participating molecule need not
be polar< but, if it is polar, then this interaction augments the dipole`dipole interaction
described above. In the dipole`induced/dipole interaction, the presence of the partial
charges of the polar molecule causes a polari&ation, or distortion, of the electron
distribution of the other molecule. #s a result of this distortion, the second molecule
acquires regions of partial positive and negative charge, and thus it becomes polar. The
partial charges so formed behave 'ust like those of a permanently polar molecule and
interact favourably with their counterparts in the polar molecule that originally induced
them. ence, the two molecules cohere. This interaction also contributes to the
intermolecular forces that are responsible for the condensation of hydrogen chloride gas.
Intermolecular forces *ispersion interaction
The third type of interaction acts between all types of molecule, polar or not. It is also
somewhat stronger than the two attractive interactions discussed thus far and is the
principal force responsible for the e!istence of the condensed phases of certain molecular
substances, such as ben&ene, other hydrocarbons, bromine, and the solid elements
phosphorus 1which consists of tetrahedral A: molecules2 and sulfur 1which consists of
crown/shaped (. molecules2. The interaction is called the dispersion interaction or, less
commonly but more revealingly, the induced/dipole`induced/dipole interaction. *onsider
two nonpolar molecules near each other. #lthough there are no permanent partial charges
on either molecule, the electron density can be thought of as ceaselessly fluctuating. #s a
result of these fluctuations, regions of equal and opposite partial charge arise in one of the
molecules and give rise to a transient dipole. This transient dipole can induce a dipole in
the neighbouring molecule, which then interacts with the original transient dipole.
#lthough the latter continuously flickers from one direction to another 1with an average
of &ero dipole overall2, the induced dipole follows it, and the two correlated dipoles
interact favourably with one another and cohere.
Intermolecular forces The hydrogen bond
The interactions described so far are not limited to molecules of any specific
composition. owever, there is one important intermolecular interaction specific to
molecules containing an o!ygen, nitrogen, or fluorine atom that is attached to a hydrogen
atom. This interaction is the hydrogen bond, an interaction of the form #@TTT8, where #
and 8 are atoms of any of the three elements mentioned above and the hydrogen atom
lies on a straight line between the nuclei of # and 8. # hydrogen bond is about -0 times
as strong as the other interactions described above, and when present it dominates all
other types of intermolecular interaction. It is responsible, for e!ample, for the e!istence
of water as a liquid at normal temperatures< because of its low molar mass, water would
be e!pected to be a gas. The hydrogen bond is also responsible for the e!istence as solids
of many organic molecules containing hydro!yl groups 1@%2< the sugars glucose and
sucrose are e!amples.
$any interpretations of the hydrogen bond have been proposed. %ne that fits into the
general scheme of this article is to think of the #@ unit as being composed of an #
atomic orbital and a hydrogen -s orbital and to consider a lone pair of electrons on 8 as
occupying a 8 orbital. When the three atoms are aligned, these three orbitals can form
three molecular orbitals> one bonding, one largely nonbonding, and one antibonding.
There are four electrons to accommodate 1two from the original #@ bond and two from
the lone pair2. They occupy the bonding and nonbonding orbitals, leaving the antibonding
orbital vacant. ence, the net effect is to lower the energy of the #8 grouping and thus
to constitute an intermolecular bond. %nce again, on encountering the hydrogen bond,
one encounters a twist in the conventional attitude< the question raised by this
interpretation is not why such a bond occurs but why it does not occur more generally.
The e!planation lies in the small si&e of the hydrogen atom, which enables the balance of
energies in the molecular orbital scheme to be favourable to bonding.
ydrogen bonding occurs to atoms other than nitrogen, o!ygen, and fluorine if they carry
a negative charge and hence are rich in readily available electrons. Thus, hydrogen
bonding is one of the principal mechanisms of hydration of anions in aqueous solution
1the bonding of 2% molecules to the solute species2 and hence contributes to the ability
of water to act as a good solvent for ionic compounds. It also contributes to the hydration
of organic compounds containing o!ygen or nitrogen atoms and thus accounts for the
much greater aqueous solubility of alcohols than hydrocarbons.
ydrogen bonds are of great significance in determining the structure of biologically
significant compounds, most notably proteins and deo!yribonucleic acid 1,9#2. #n
important feature of the structure of proteins 1which are polypeptides, or polymers
formed from amino acids2 is the e!istence of the peptide link, the group @*%@9@,
which appears between each pair of ad'acent amino acids. This link provides an 9
group that can form a hydrogen bond to a suitable acceptor atom and an o!ygen atom,
which can act as a suitable receptor. Therefore, a peptide link provides the two essential
ingredients of a hydrogen bond. The keying together of such peptide groups by hydrogen
bonding of the type shown in )igure -V was e!amined in detail by
Aauling and 3obert *orey, who formulated a set of rules, the Aauling/*orey rules, for its
implementation. The implication of these rules is the e!istence of two types of structure
for a polypeptide, which is either a helical form 1the a heli!2 or a pleated sheet form 1the
b/pleated sheet2. #ll polypeptides have one structure or the other and often have
alternating regions of each. (ince the properties and behaviour of an en&yme molecule 1a
particular class of polypeptides2 are determined by its shape and, in particular, by the
shape of the region where the molecule it acts on needs to attach, it follows that hydrogen
bonds are centrally important to the functions of life.
ydrogen bonds are also responsible for the transmission of genetic information from
one generation to another, for they are responsible for the specific keying together of
cytosine with guanine and thymine with adenine moieties that characteri&es the structure
of the ,9# double heli!.
Varieties of solids
*hemical bonds and intermolecular forces are 'ointly responsible for the e!istence of the
solid phases of matter. This section reviews some of the types of solid that are
encountered and relates them to the topics discussed earlier.
)arieties of solids Ionic solids
The structures of ionic solids have already been described in some detail. They consist of
individual ions that are stacked together in such a way that the assembly has the lowest
possible energy. These ions may be monatomic 1as in sodium chloride, which consists of
9a
?
and *l
@
ions2 or the ions may themselves be covalently bonded polyatomic species.
#n e!ample of the latter is ammonium nitrate, in which the cation is 9:
?
and the anion
is 9%;
@
< the 9@ and 9@% bonds within the ions are covalent. Ionic compounds are
generally hard and brittle and have high melting points.
)arieties of solids Molecular solids
The structures of molecular solids, which are solids composed of individual molecules,
have also been touched on in the section on intermolecular forces. These molecules are
held to one another by hydrogen bonds 1if they can form them2, dispersion forces, and
other dipolar forces"in that order of decreasing importance"and the molecules stack
together in a pattern that minimi&es their total energy. 5!amples of such solids include
ice, in which hydrogen bonding is of paramount importance, and polyethylene, in which
dispersion forces are dominant. Bnless hydrogen bonds are present 1in which case
molecular solids resemble ionic solids in brittleness2, molecular solids are generally soft
and have low melting points because the bonds between the molecules are easily
overcome.
)arieties of solids ,etwor$ solids
There e!ists a class of solids called network solids in which the bonding is essentially due
to a network of covalent bonds that e!tends throughout the solid. (uch solids are hard and
rigid and have high melting points because the crystal is like one enormous molecule.
The most well/known e!ample of a network solid is diamond, which consists of
tetrahedrally bonded carbon atoms 1see )igure V2. 8y virtue of the rigidity of its bonding
structure, diamond is the hardest substance known and also the best conductor of heat.
(ome solids have a network character in certain directions and a more molecular
character in other directions. %nce again, carbon provides the paradigm e!ample, for the
form of carbon known as graphite consists of a stack of sheets of he!agonal rings of
carbon atoms. In the plane of the sheets, the bonding is covalent 1and resembles an
e!tended version of the bonding in ben&ene2. The sheets themselves are held together by
binding that is so weak that it is sometimes referred to as a van der Waals interaction. The
anisotropy of the structure of graphite accounts for the anisotropy of its electrical
conductivity 1which is higher in the plane of the sheets than perpendicular to them2. The
ability of graphite to shed sheets of carbon 1a feature utili&ed in the manufacture of
pencils2 and to act as a high/temperature lubricant 1because the sheets can slide over one
another2 appears to be consistent with this structure but in fact seems to depend on the
presence of impurities between the sheets.
)arieties of solids Metals
The remaining ma'or type of solid is a metal. # metal is characteri&ed by its lustre, the
ease with which it may be deformed 1rather than shattered2 by hammering, and its high
electrical and thermal conductivities. $etals also tend to have higher densities than other
types of solid. The starting point for theories of the structures of metals is to regard them
as consisting of cations of the metal atoms embedded in a sea formed by the discarded
valence electrons. The mobility of these electrons accounts for the mechanical, optical,
and electrical properties of metals. The spherical cations can pack closely together yet
still give rise to locally neutral electrical assemblies. This is because of the ability of the
electrons to spread between the cations and neutrali&e their charges regardless of how
closely they are packed. The closeness of the packing of the atoms accounts for the high
densities of metals.
In the conte!t of theories of the chemical bond, a metal is one e!tremely large
homonuclear molecule. 1)or an alternative point of view, see the article crystal2 If a
sample of sodium metal is thought of as consisting of n sodium atoms where each atom
has a ;s orbital for use in the construction of molecular orbitals and each atom supplies
one electron to a common pool, then from these n atomic orbitals n molecular orbitals can
be constructed. 5ach orbital has a characteristic energy, and the range of energies spanned
by the n orbitals is finite, however great the value of n. If n is very large, it follows that
the energy separation between neighbouring molecular orbitals is very small and
approaches &ero as n approaches infinity. The molecular orbitals then form a band of
energies. #nother similar band can be formed by the overlap of the ;p orbitals of the
atoms, but there is a substantial band gap"i.e., a region of energy in which there are no
molecular orbitals"between the two bands.
#lthough the ;s band is virtually continuous, it actually consists of n discrete molecular
orbitals, each of which, by the Aauli e!clusion principle, can contain two paired electrons.
It follows that the ;s band of sodium, which is occupied by the pool of n electrons, is
only half full. There are empty molecular orbitals immediately above the uppermost filled
orbitals, and it is easy for a perturbation, such as an applied potential difference or an
oscillating electromagnetic field of incident light, to move the electrons into these
unoccupied levels. ence, the electrons are very mobile and can conduct an electric
current, reflect light, transmit energy, and rapidly migrate to new locations when the
cations are moved by hammering.
The full theory of the structure of metals is a highly technical sub'ect 1as are the full
theories of the other topics discussed here2. This brief introduction has been intended
only to show that the ideas of molecular orbital theory can be naturally e!tended to
account for the general features of the structures and properties of solids.
Advanced aspects of chemical bonding
This section treats several aspects of molecular structure that are of more speciali&ed
interest and shows how particular classes of compounds are described. $olecular orbital
theory will be used as a framework for the discussion, but aspects of valence bond theory
will be incorporated when it is natural 1in the sense of being commonplace in chemistry2
to use them.
Advanced aspects of chemical bonding Theories of bonding in comple-es
# particular class of compounds that once gave rise to some difficulty in the e!planation
of the origin of their bonding are the comple!es of transition metal ions. There are
numerous e!amples of such species< they have in common a structure in which a central
metal ion is surrounded by a number of ions or molecules, called ligands, that can also
e!ist separately. The most common comple!es have si! ligands arranged in an octahedron
around the central ion. #n e!ample is O)e12%27P
2?
, where )e denotes iron. This species
can essentially be regarded as an )e
2?
ion, with an electron configuration O#rP;d
7
,
surrounded by si! 2% molecules linked to the metal ion through their o!ygen atoms.
*omple! formation is an e!ample of a particular class of reactions known as 0ewis acid/
base reactions. The general form of 0ewis acid/base reactions involves the formation of a
covalent bond between a species that supplies an electron pair, which is called a 0ewis
base, and a species that can accept an electron pair, which is called a 0ewis acid. In
comple!es of the formula O$12%27P
n?
, the central metal ion acts as the 0ewis acid and
the ligand molecules act as the 0ewis bases by virtue of a lone pair of electrons on the
o!ygen atom 1only one of the lone pairs is in a position to act in this way2. In general, a
0ewis acid/base reaction is represented by the scheme # ? >8 W #@8. (uch reactions
occur widely in chemistry, but the singular characteristic of metal ions is that they can act
as acceptors to several ligands. The actual number of ligands that attach to a metal ion is
in part controlled by the spatial problem of packing ligands together around a central ion.
!dvanced aspects of chemical bonding Theories of bonding in comple0es
#rystal field theory
#lthough comple! formation is an e!ample of the linking together of species by the
formation of covalent 1but highly polar2 bonds, the first systematic approach to the
e!planation of the properties of comple!es was based on a model in which the effect of
the ligands was treated as an essentially ionic problem. In this crystal field theory, each
ligand was represented by a negative point charge. 1This point charge models the lone
pair of electrons that is responsible for the bond formation.2 There are then two
contributions to the binding energy. %ne is the electrostatic attraction between the central
cation and the negative point charges, which is largely responsible for the stability of the
comple!. There is also the differential effect of the array of the point charges on the
energies of the d orbitals of the ion. Whereas in a free atom all five d orbitals have the
same energy, in an octahedral crystal field they split into two groups 1)igure -.
2, with three orbitals 1labeled t2g< the labeling is based on details of their
symmetry2 lower in energy than the remaining two 1labeled eg2. The difference in energy
between the two sets is denoted c and is called the crystal/field splitting energy 1*)(52.
This energy is the parameter that is used to correlate a variety of spectroscopic,
thermodynamic, and magnetic properties of comple!es.
The essential feature of crystal field theory is that there is a competition between the
magnitude of the *)(5 and the pairing energy, which is the energy required to
accommodate two electrons in one orbital. When the pairing energy is high compared
with the *)(5, the lowest/energy electron configuration is achieved with as many
electrons as possible in different orbitals. The arrangement of a d
Q
ion, for instance, is
t2g
;
eg
2
, with all spins parallel 1as in )igure -.82. owever, if the ligands give rise to a
very strong crystal field, so that the *)(5 is large compared with the pairing energy, then
the lowest/energy electron configuration is that with as many electrons as possible in the
lower 1t2g2 set of orbitals. In such a case, a ;d
Q
ion would adopt the configuration t2g
Q
, with
only one unpaired spin as in )igure -.#. Thus, because magnetism arises from the
presence of electron spins, it can be seen that the magnetic properties of the comple! can
be correlated with the si&e of the *)(5. The same is true of spectroscopic and
thermodynamic properties. In particular it is found that ligands can be arranged in order
of the strength of the crystal field that they generate, and this so/called spectrochemical
series can be used to rationali&e and predict the properties of comple!es.
!dvanced aspects of chemical bonding Theories of bonding in comple0es
$igand field theory
*rystal field theory is an artificial parameteri&ation of the bonding in comple!es, for it
models the actual bonding in terms of an array of point charges. # superior theory is a
modification of crystal field theory known as ligand field theory, which is more securely
based in $% theory and allows for a more appropriate degree of delocali&ation of
electrons over the metal ion and the ligands.
In essence, in ligand field theory molecular orbitals of comple!es of first/transition/series
1i.e., period/:2 metals are constructed from the five ;d orbitals of the central metal cation
and one orbital from each of the si! ligand atoms that are directly attached to the metal
cation. It follows that in such an octahedral comple! there are Q ? 7 G -- molecular
orbitals to accommodate the ;d electrons of an O#rP;d
n
species and -2 electrons from the
si! ligand atoms, giving -2 ? n electrons in all. The -- $%s span a range of energies.
Twelve of the electrons occupy the si! lowest/energy $%s, which are largely ligand/
atom in character. The remaining n electrons are to be accommodated in the eg and t2g sets
of orbitals. The energy separation between these two sets of orbitals, the ligand/field
splitting energy 10)(52 is the ligand field version of the *)(5 in crystal field theory, and
from this point on the construction of the lowest/energy electron configuration is much
the same as in crystal field theory. owever, ligand field theory is less artificial, allows
for electron delocali&ation, and is more readily e!tended to more comple! patterns of
bonding between the central metal ion and the ligands 1such as the incorporation of bonds
with ] symmetry2.
!dvanced aspects of chemical bonding #ompounds displaying unique
bonding /rganometallic compounds
# particular class of comple!es consists of the organometallic compounds, in which there
are bonds between a metal atom and a carbon atom. #mong the most important of such
compounds are the carbonyls, which are comple!es in which one or more of the ligands
is a carbon mono!ide molecule, *%, either linked to one atom or bridging two. #nother
interesting class of organometallic compounds is composed of the metallocenes,
informally called Esandwich compounds,F in which the metal atom sits between two
planar hydrocarbon rings, analogous to the meat in a sandwich. %f these, ferrocene
O)e1*QQ22P was among the first to be synthesi&ed.
The stabilities of organometallic compounds follow certain empirical rules, among which
the -./electron rule is the analogue of the octet rule of main/group compounds.
#ccording to this rule, the most stable organometallic compounds are those having -.
electrons in the valence shell, a term in this conte!t e!tended to include the outermost d
orbitals. 9ickel tetracarbonyl, 9i1*%2:, a poisonous gas used in the refining of nickel, has
-0 electrons provided by the neutral nickel atom and two from each of the four *%
ligands, giving -. electrons in all.
The electronic structures of organometallic compounds can be e!pressed most effectively
in $% terms, and they can be regarded as no more than a special case of ligand field
theory. There are certain details that make them particularly interesting, however. To give
a sense of the detail in which the structure of a metal/carbon bond may be e!pressed,
attention will be focused here on the link between a metal atom 1$2 and a carbonyl group
1*%2> $@*%.
# *% molecule has much the same electronic structure as an 92 molecule, because it has
the same number of electrons"that is, the two species are isoelectronic. There are two
important features of this structure, which differ in detail from 92 on account of the
different electronegativities of the two elements in *%. %ne is that the highest occupied
molecular orbital, the %$%, is largely confined to the carbon atom and can be
interpreted as being a lone pair occupying an orbital with \ symmetry. This lone pair
enables *% to act as a 0ewis base and to link to the metal atom by forming a \ bond to it
by overlap with one of the lobes of a d orbital. owever, the lowest unfilled molecular
orbital, the 0B$%, has ] symmetry and can accept electrons from an appropriate d
orbital of the metal, and thus it can help the ligand to act as a 0ewis acid. It is this ability
of the ligand to act as both a 0ewis base and a 0ewis acid that is responsible for the
stability of metal carbonyls.
!dvanced aspects of chemical bonding #ompounds displaying unique
bonding %oranes
The electron/deficient compound diborane, 827, as noted earlier, can be regarded as a
cluster of atoms held together by pairs of delocali&ed electrons that e!tend their binding
influence over all electrons in the molecule. The unusual feature of diborane is the
e!istence of 8@@8 bridges as part of the cluster. #lthough an $% treatment of the
molecule deals with it as a whole, chemists find it helpful to focus on this novel feature
and to consider each 8@@8 moiety as an e!ample of a three/centre, two/electron bond
1a ;c,2e bond, as shown in )igure -= 2. They regard diborane as three
atoms held together by a pair of electrons delocali&ed over three atoms but are aware that
this semilocali&ed picture is only a part of the true picture.
The usefulness of the concept of a ;c,2e bond stems from two observations. The first is
that diborane is in fact only one of a large class of compounds of boron and hydrogen, the
boranes and the borohydride anions, in which the same feature is found. The second
observation is that a ;c,2e bond can be formed by three boron atoms. Intricate networks
of atoms can be formed in this way"for e!ample, some having the form of closed
frameworks 1the closo/boranes2, some looking like untidy birds4 nests 1the nido/boranes2,
and some resembling spiderwebs 1the arachno/boranes2. Which type of structure is
obtained correlates with the number of valence electrons in the molecule, and the
correlation is e!pressed by Wade4s rules. These rules are empirical, but they can be
'ustified by a consideration of the numbers of ;c,2e and ordinary 2c,2e bonds that are
needed in each type of structure. They constitute an e!cellent e!ample of how chemists
utili&e the concept of bond formation and deploy a mi!ture of valence bond and
molecular orbital concepts to establish or rationali&e helpful correlations between the
number of electrons present and the structure of the species.
!dvanced aspects of chemical bonding #ompounds displaying unique
bonding )etal cluster compounds
# metal cluster compound is one in which metal atoms are linked directly to one another
1)igure 20 2. # simple e!ample is the ion g2
2?
, in which two mercury
1g2 ions are linked together. # slightly more elaborate version is the ion O3e2*l.P
2@
, in
which there is a direct link between two rhenium 13e2 atoms. (ome metal cluster
compounds have more than two metal atoms< an e!ample is O3e;*l-2P
;@
, in which there
are three rhenium atoms bonded together. It is sometimes difficult to determine whether
the metal atoms are indeed directly linked or merely held quite close together by a
framework of bridging ligands.
$etal cluster compounds warrant a special mention here because they provide the only
e!amples of quadruple bonds in chemistry. #part from that, their bonding can be treated
as a straightforward e!ercise in $% or Y8 theory. Indeed, a metal cluster can be regarded
as an e!ceedingly tiny sample of metal, with insufficient atoms present for the molecular
orbitals to form a continuous band. The structure of O3e2*l.P
2@
is shown in )igure 20. The
clue to the e!istence of unusual bonding is the arrangement of the two sets of chloride
ligands> to minimi&e repulsions between the atoms, each 3e*l: group might be e!pected
to be twisted :QZ relative to the ne!t rather than being in the orientation shown. There
appears to be a bonding feature between the two rhenium atoms that holds the groups as
illustrated. This feature is taken to be a quadruple bond arising from the overlap of d
orbitals on the two rhenium atoms.
%ne component in the structure of a quadruple bond is a \ bond formed by the
cylindrically symmetrical overlap of two d orbitals. There are also two ] bonds formed
by the overlap of two appropriately orientated d orbitals. The new feature is the d bond,
which is formed by the face/to/face overlap of two parallel d orbitals and has a distinctly
different symmetry with respect to the internuclear a!is than the other two types of bond.
# quadruple bond therefore consists of a \ bond, two ] bonds, and one d bond. The
reduction in bond strength that would occur if one d orbital were rotated away from its
partner so that overlap is lessened accounts for the torsional rigidity of the bond and the
observed shape of the species.
Advanced aspects of chemical bonding 'omputational approaches to molecular
structure
In conclusion, a brief introduction to the manner in which these qualitative ideas are
implemented computationally follows. The computation of molecular structures by
numerical solution of the (chrHdinger equation is a highly developed discipline. The
principal difficulty is the large number of interactions between electrons that must be
taken into account< this fact makes computational quantum chemists some of the most
demanding users of computers and, increasingly, of supercomputers.
There are two strands of approach to the computation of molecular structure. In the
semiempirical approach, the calculation draws on a number of e!perimentally determined
characteristics to help in the overall calculation. In the ab initio approach, the calculation
proceeds from first principles 1the (chrHdinger equation2 and makes no use of imported
information. The former approach was dominant in the -=V0s, but increases in computing
power have led to an ascendancy of ab initio techniques since then. The latter are
intrinsically more reliable because there can be no certainty that a quantity determined in
one conte!t is appropriate to a particular molecule.
The central aim of computations is to identify the lowest/energy arrangement of a given
set of atoms and to identify that arrangement as the structure of the molecule. The
calculational strategy adopted is to seek self/consistency in the calculation, and, for that
reason, the computations are referred to as self/consistent field 1(*)2 procedures. Thus, a
particular electronic distribution is proposed, and the distribution of the electrons is
recalculated on the basis of this first appro!imation. The distribution is then calculated
again on the basis of that improved description, and the process is continued until there is
negligible change"i.e., until the electron distribution has achieved self/consistency.
The implementation of this basic strategy can take a number of forms, and rival
techniques have given rise to a large number of acronyms, such as #$- 1#ustin $ethod
-2 and $I9,% 1$odified Intermediate 9eglect of ,ifferential %verlap2, which are two
popular semiempirical procedures.
With self/consistency established, the wavefunctions are available for detailed scrutiny.
%ne illustration must suffice. There is certain evidence that carcinogenic or
pharmacological activity correlates with certain aspects of the charge distribution in
molecules. Instead of dealing with the primitive concept of partial charges, numerical
wavefunctions can be used to map the details of the charge distribution and hence to
screen molecules for possible activity. This approach is potentially of considerable utility
for pharmaceutical products as it can help to reduce the amount of in vivo screening of
novel products.
*omputational procedures have advanced to the stage where the role of the environment
1for e!ample, the water around en&yme molecules2 can be incorporated. They are also
being applied to the demanding calculations that are needed to describe the replacement
of one grouping of chemical bonds into another that takes place in the course of chemical
reactions. Thus, as well as dealing with the static considerations of structure, modern
treatments of the chemical bond are now confronting the dynamic problems of reactions.
Additional (eading
#n elementary introduction to chemical bonding is found in A.W. #tkins and 6.#. 8eran,
General Chemistry, 2nd ed. 1-==22. Aictorial interpretations of many of the quantum
mechanical concepts mentioned in this article are available in A.W. #tkins, Quanta: A
Handbook of Concepts, 2nd ed. 1-==22. 3.6. Auddephatt and A.C. $onaghan, he
!eriodic able of the "lements, 2nd ed. 1-=.72, provides an introduction to the basis of
chemical periodicity. ,uward ). (hriver, A.W. #tkins, and *ooper . 0angford,
#nor$anic Chemistry, 2nd ed. 1-==:2, includes descriptions of atomic structure and
bonding in comple!es, clusters, and electron/deficient compounds. Two authoritative
monographs on bonding are 0inus Aauling, he %ature of the Chemical &ond and the
'tructure of (olecules and Crystals, ;rd ed. 1-=70, reissued -=.=2< and *.#. *oulson,
Coulson)s *alence, ;rd ed. by 3oy $cWeeny 1-=V=2. # more physical view of chemical
bonding than presented in this article is given by 6ohn *. $orrison et al., E5lectronic
(tructure of #toms and $olecules,F in +eorge 0. Trigg 1ed.2, "ncyclopedia of Applied
!hysics, vol. 7 1-==;2, pp. :Q`=.. %ther accounts include 3oger 0. ,eCock and arry 8.
+ray, Chemical 'tructure and &ondin$ 1-=.02< 8rian Webster, Chemical &ondin$ heory
1-==02< and #hmed eewail 1ed.2, he Chemical &ond: 'tructure and +ynamics 1-==22.
#pplications to pharmacologically active molecules are introduced in W.+. 3ichards,
Quantum !harmacolo$y, 2nd ed. 1-=.;2. *omputational aspects of the chemical bond are
described in #lan inchliffe, Computational Quantum Chemistry 1-=..2.