Chemical bonding

A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two or more atoms. The bond is caused by the electromagnetic force attraction between opposite charges, either between electrons and nuclei, or as the result of a dipole attraction. The strength of chemical bonds varies considerably; there are "strong bonds" such as covalent or ionic bonds and "weak bonds" such as dipole-dipole interactions, the London dispersion force and hydrogen bonding.

Since opposite charges attract via a simple electromagnetic force, the negatively charged electrons orbiting the nucleus and the positively charged protons in the nucleus attract each other. Also, an electron positioned between two nuclei will be attracted to both of them. Thus, the most stable configuration of nuclei and electrons is one in which the electrons spend more time between nuclei, than anywhere else in space. These electrons cause the nuclei to be attracted to each other, and this attraction results in the bond. However, this assembly cannot collapse to a size dictated by the volumes of these individual particles. Due to the matter wave nature of electrons and their smaller mass, they occupy a much larger amount of volume compared with the nuclei, and this volume occupied by the electrons keeps the atomic nuclei relatively far apart, as compared with the size of the nuclei themselves.

In general, strong chemical bonding is associated with the sharing or transfer of electrons between the participating atoms. The atoms in molecules, crystals, metals and diatomic gases indeed most of the physical environment around us are held together by chemical bonds, which dictate the structure of matter.

 Overview of main types of chemical bonds

In the simplest view of a so-called 'covalent' bond, one or more electrons (often a pair of electrons) are drawn into the space between the two atomic nuclei. Here the negatively charged electrons are attracted to the positive charges of both nuclei, instead of just their own. This overcomes the repulsion between the two positively charged nuclei of the two atoms, and so this overwhelming attraction holds the two nuclei in a fixed configuration of equilibrium, even though they will still vibrate at equilibrium position. In summary, covalent bonding involves sharing of electrons in which the positively charged nuclei of two or more atoms simultaneously attract the negatively charged electrons that are being shared. In a polar covalent bond, one or more electrons are unequally shared between two nuclei.

In a simplified view of an ionic bond, the bonding electron is not shared at all, but transferred. In this type of bond, the outer atomic orbital of one atom has a vacancy which allows addition of one or more electrons. These newly added electrons potentially occupy a lower energy-state (effectively closer to more nuclear charge) than they experience in a different atom. Thus, one nucleus offers a more tightly bound position to an electron than does another nucleus, with the result that one atom may transfer an electron to the other. This transfer causes one atom to assume a net positive charge, and the other to assume a net negative charge. The bond then results from electrostatic attraction between atoms, and the atoms become positive or negatively charged ions.

The last and rarely mentioned type of bonding is metallic bond.

All bonds can be explained by quantum theory, but, in practice, simplification rules allow chemists to predict the strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are two examples. More sophisticated theories are valence bond theory which includes orbital hybridization and resonance, and the linear combination of atomic orbitals molecular orbital method which includes ligand field theory. Electrostatics are used to describe bond polarities and the effects they have on chemical substances.

Valance bond theory

In chemistry, valence bond (VB) theory is one of two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of the dissociated atoms combine to give individual chemical bonds when a molecule is formed. In contrast, molecular orbital theory has orbitals that cover the whole molecule.[1]

Theory of valance bond

According to this theory a covalent bond is formed between the two atoms by the overlap of half filled valence atomic orbitals of each atom containing one unpaired electron. A valence bond structure is similar to a Lewis structure, but where a single Lewis structure cannot be written, several valence bond structures are used. Each of these VB structures represents a specific Lewis structure. This combination of valence bond structures is the main point of resonance theory. Valence bond theory considers that the overlapping atomic orbitals of the participating atoms form a chemical bond. Because of the overlapping, it is most probable that electrons should be in the bond region. Valence bond theory views

bonds as weakly coupled orbitals (small overlap). Valence bond theory is typically easier to employ in ground state molecules.

The overlapping atomic orbitals can differ. The two types of overlapping orbitals are sigma and pi. Sigma bonds occur when the orbitals of two shared electrons overlap head-to-head. Pi bonds occur when two orbitals overlap when they are parallel. For example, a bond between two s-orbital electrons is a sigma bond, because two spheres are always coaxial. In terms of bond order, single bonds have one sigma bond, double bonds consist of one sigma bond and one pi bond, and triple bonds contain one sigma bond and two pi bonds. However, the atomic orbitals for bonding may be hybrids. Often, the bonding atomic orbitals have a character of several possible types of orbitals. The methods to get an atomic orbital with the proper character for the bonding is called hybridization.

VB theory today
Valence bond theory now complements molecular orbital (MO) theory, which does not adhere to the VB idea that electron pairs are localized between two specific atoms in a molecule but that they are distributed in sets of molecular orbitals which can extend over the entire molecule. MO theory can predict magnetic properties in a straightforward manner, while valence bond theory gives similar results but is more complicated. Valence bond theory views aromatic properties of molecules as due to resonance between Kekule, Dewar and possibly ionic structures, while molecular orbital theory views it as delocalization of the electrons. The underlying mathematics are also more complicated limiting VB treatment to relatively small molecules. On the other hand, VB theory provides a much more accurate picture of the reorganization of electronic charge that takes place when bonds are broken and formed during the course of a chemical reaction. In particular, valence bond theory correctly predicts the dissociation of homonuclear diatomic molecules into separate atoms, while simple molecular orbital theory predicts dissociation into a mixture of atoms and ions.

More recently, several groups have developed what is often called modern valence bond theory. This replaces the overlapping atomic orbitals by overlapping valence bond orbitals that are expanded over a large number of basis functions, either centered each on one atom to give a classical valence bond picture, or centered on all atoms in the molecule. The resulting energies are more competitive with energies from calculations where electron correlation is introduced based on a Hartree-Fock reference wavefunction. The most recent text is by Shaik and Hiberty.[4]

Applications of VB theory
An important aspect of the VB theory is the condition of maximum overlap which leads to the formation of the strongest possible bonds. This theory is used to explain the covalent bond formation in many molecules.

For Example in the case of the F2 molecule the F - F bond is formed by the overlap of pz orbitals of the two F atoms, each containing an unpaired electron. Since the natures of the overlapping orbitals are different in H2 and F2 molecules, the bond strength and bond lengths differ between H2 and F2 molecules.

In an HF molecule the covalent bond is formed by the overlap of the 1s orbital of H and the 2pz orbital of F, each containing an unpaired electron. Mutual sharing of electrons between H and F results in a covalent bond in HF.

 Comparison of valence bond and molecular orbital theory

In some respects valence bond theory is superior to molecular orbital theory. When applied to the simplest two-electron molecule, H2, valence bond theory, even at the simplest Heitler-London approach, gives a much closer approximation to the bond energy, and it provides a much more accurate representation of the behavior of the electrons as chemical bonds are formed and broken. In contrast simple molecular orbital theory predicts that the hydrogen molecule dissociates into a linear superposition of hydrogen atoms and positive and negative hydrogen ions, a completely unphysical result. This explains in part why the curve of total energy against interatomic distance for the valence bond method lies above the curve for the molecular orbital method at all distances and most particularly so for large distances. This situation arises for all homonuclear diatomic molecules and is particularly a problem for F2, where the minimum energy of the curve with molecular orbital theory is still higher in energy than the energy of two F atoms.

The concepts of hybridization are so versatile, and the variability in bonding in most organic compounds is so modest, that valence bond theory remains an integral part of the vocabulary of organic chemistry. However, the work of Friedrich Hund, Robert Mulliken, and Gerhard Herzberg showed that molecular orbital theory provided a more appropriate description of the spectroscopic, ionization and magnetic properties of molecules. The deficiencies of valence bond theory became apparent when hypervalent molecules (e.g. PF5) were explained without the use of d orbitals that were crucial to the bonding hybridisation scheme proposed for such molecules by Pauling. Metal complexes and electron deficient compounds (e.g. diborane) also appeared to be well described by molecular orbital theory, although valence bond descriptions have been made.

In the 1930s the two methods strongly competed until it was realised that they are both approximations to a better theory. If we take the simple valence bond structure and mix in all possible covalent and ionic structures arising from a particular set of atomic orbitals, we reach what is called the full configuration interaction wave function. If we take the simple molecular orbital description of the ground state and combine that function with the functions describing all possible excited states using unoccupied orbitals arising from the same set of atomic orbitals, we also reach the full configuration interaction wavefunction. It can be then seen that the simple molecular orbital approach gives too much weight to the ionic structures, while the simple valence bond approach gives too little. This can also be described as saying that the molecular orbital approach is too delocalised, while the valence bond approach is too localised.

The two approaches are now regarded as complementary, each providing its own insights into the problem of chemical bonding. Modern calculations in quantum chemistry usually start from (but ultimately go far beyond) a molecular orbital rather than a valence bond approach, not because of any intrinsic superiority in the former but rather because the MO approach is more readily adapted to numerical computations. However better valence bond programs are now available.

Bonds in chemical formulas

The fact that atoms and molecules are three-dimensional makes it difficult to use a single technique for indicating orbitals and bonds. In molecular formulas the chemical bonds (binding orbitals) between atoms are indicated by various different methods according to the type of discussion. Sometimes, they are completely neglected. For example, in organic chemistry chemists are sometimes concerned only with the functional groups of the molecule. Thus, the molecular formula of ethanol (a compound in alcoholic beverages) may be written in a paper in conformational, three-dimensional, full two-dimensional (indicating every bond

with no three-dimensional directions), compressed two-dimensional (CH3CH2 OH), separating the functional group from another part of the molecule (C2H5OH), or by its atomic constituents (C2H6O), according to what is discussed. Sometimes, even the non-bonding valence shell electrons (with the twodimensional approximate directions) are marked, i.e. for elemental carbon .'C'. Some chemists may also mark the respective orbitals, i.e. the hypothetical ethene4 anion (\/C=C/\ 4) indicating the possibility of bond formation. [edit] Strong chemical bondsTypical bond lengths in pm and bond energies in kJ/mol. Bond lengths can be converted to by division by 100 (1 = 100 pm). Data taken from [1]. Bond Length (pm) Energy (kJ/mol) H Hydrogen HH 74 HO 96 HF 92 HCl 127 C Carbon CH 109 CC 154 413 348 436 366 568 432

C=C

134

614 839 308 360 488 330

CC 120 CN 147 CO 143 CF 134

CCl 177

N Nitrogen NH 101 NN 145 NN 110 O Oxygen OO 148 O=O 121 145 498 391 170 945

F, Cl, Br, I Halogens FF 142 158 243 366 193 298 151

ClCl 199 BrH 141 BrBr 228 IH II 161 267

Strong chemical bonds are the intramolecular forces which hold atoms together in molecules. A strong chemical bond is formed from the transfer or sharing of electrons between atomic centers and relies on the electrostatic attraction between the protons in nuclei and the electrons in the orbitals. Although these bonds typically involve the transfer of integer numbers of electrons (this is the bond order, which respresents one transferred electron or two shared electrons), some systems can have intermediate numbers of bonds. An example of this is the organic molecule benzene, where the bond order is 1.5 for each carbon atom, meaning that it has 1.5 bonds (shares three electrons) with each one of its two neighbors.

The types of strong bond differ due to the difference in electronegativity of the constituent elements. A large difference in electronegativity leads to more polar (ionic) character in the bond.

Covalent bond
Covalent bonding is a common type of bonding, in which the electronegativity difference between the bonded atoms is small or nonexistent. Bonds within most organic compounds are described as covalent. See sigma bonds and pi bonds for LCAO-description of such bonding.

A polar covalent bond is a covalent bond with a significant ionic character. This means that the electrons are closer to one of the atoms than the other, creating an imbalance of charge. They occur as a bond between two atoms with moderately different electronegativities, and give rise to dipole-dipole interactions. The electronegativity of these bonds is 0.3 to 1.7 .

A coordinate covalent bond is one where both bonding electrons are from one of the atoms involved in the bond. These bonds give rise to Lewis acids and bases. The electrons are shared roughly equally between the atoms in contrast to ionic bonding. Such bonding occurs in molecules such as the ammonium ion (NH4+) and are shown by an arrow pointing to the Lewis acid. Also known as non-polar covalent bond, the electronegativity of these bonds range from 0 to 0.3.

Molecules which are formed primarily from non-polar covalent bonds are often immiscible in water or other polar solvents, but much more soluble in non-polar solvents such as hexane.

Ionic bond

Ionic bonding is a type of electrostatic interaction between atoms which have a large electronegativity difference. There is no precise value that distinguishes ionic from covalent bonding, but a difference of electronegativity of over 1.7 is likely to be ionic, and a difference of less than 1.7 is likely to be covalent.[4] Ionic bonding leads to separate positive and negative ions. Ionic charges are commonly between 3e to +3e. Ionic bonding commonly occurs in metal salts such as sodium chloride (table salt). A typical feature of ionic bonds is that the species form into ionic crystals, in which no ion is specifically paired with any single other ion, in a specific directional bond. Rather, each species of ion is surrounded by ions of the opposite charge, and the spacing between it and each of the oppositely charged ions near it, is the same for all surrounding atoms of the same type. It is thus no longer possible to associate an ion with any specific other single ionized atom near it. This is a situation unlike that in covalent crystals, where covalent bonds between specific atoms are still discernable from the shorter distances between them, as measured by with such techniques as X-ray diffraction.

Ionic crystals may contain a mixture of covalent and ionic species, as for example salts of complex acids, such as sodium cyanide, NaCN. Many minerals are of this type. X-ray diffration shows that in NaCN, for example, the bonds between sodium cations (Na+) and the cyanide anions (CN-) are ionic, with no sodium ion associated with any particular cyanide. However, the bonds between C and N atoms in cyanide are of the covalent type, making each of the carbon and nitrogen associated with just one of its opposite type, to which it is physically much closer than it is to other carbons or nitrogens in a sodium cyanide crystal.

When such salts dissolve into water, the ionic bonds are typically broken by the interaction with water, but the covalent bonds continue to hold. In solution, the cyanide ions, still bound together as single CN- ions, move independently through the solution, as do sodium ions, as Na+. These charged ions move apart because each of them are more strongly attracted to a number of water molecules, than to each other. The attraction between ions and water molecules in such solutions is due to a type of weak dipole-dipole type chemical bond.

One- and three-electron bonds

Bonds with one or three electrons can be found in radical species, which have an odd number of electrons. The simplest example of a 1-electron bond is found in the hydrogen molecular cation, H2+. One-electron bonds often have about half the bond energy of a 2-electron bond, and are therefore called "half bonds". However, there are exceptions: in the case of dilithium, the bond is actually stronger for the 1-electron Li2+ than for the 2-electron Li2. This exception can be explained in terms of hybridization and inner-shell effects.[5]

The simplest example of three-electron bonding can be found in the helium dimer cation, He2+, and can also be considered a "half bond" because, in molecular orbital terms, the third electron is in an anti-bonding orbital which cancels out half of the bond formed by the other two electrons. Another example of a molecule containing a 3-electron bond, in addition to two 2-electron bonds, is nitric oxide, NO. The oxygen molecule, O2 can also be regarded as having two 3electron bonds and one 2-electron bond, which accounts for its paramagnetism and its formal bond order of 2.[6]

Molecules with odd-electron bonds are usually highly reactive. These types of bond are only stable between atoms with similar electronegativities.[6]

Bent bond
Bent bonds, also known as banana bonds, are bonds in strained or otherwise sterically hindered molecules whose binding orbitals are forced into a banana-like form. Bent bonds are often more susceptible to reactions than ordinary bonds.

3c-2e and 3c-4e bonds

In three-center two-electron bonds ("3c2e") three atoms share two electrons in bonding. This type of bonding occurs in electron deficient compounds like diborane. Each such bond (2 per molecule in diborane) contains a pair of electrons which connect the boron atoms to each other in a banana shape, with a proton (nucleus of a hydrogen atom) in the middle of the bond, sharing electrons with both boron atoms.

Three-center four-electron bonds ("3c4e") also exist which explain the bonding in hypervalent molecules. In certain cluster compounds, so-called four-center two-electron bonds also have been postulated.

In certain conjugated (pi) systems, such as benzene and other aromatic compounds (see below), and in conjugated network solids such as graphite, the electrons in the conjugated system of -bonds are spread over as many nuclear centers as exist in the molecule, or the network.

Aromatic bond
In organic chemistry, certain configurations of electrons and orbitals infer extra stability to a molecule. This occurs when orbitals overlap and combine with others on different atomic centres, forming a long range bond. For a molecule to be aromatic, it must obey Hckel's rule, where the number of electrons fit the formula 4n + 2, where n is an integer. The bonds involved in the aromaticity are all planar.

In benzene, the prototypical aromatic compound, 18 (n = 4) bonding electrons bind 6 carbon atoms together to form a planar ring structure. The bond "order" (average number of bonds) between the different carbon atoms may be said to be (18/6)/2=1.5, but in this case the bonds are all identical from the chemical point of view. They may sometimes be written as single bonds alternating with double bonds, but the view of all ring bonds as being equivalently about 1.5 bonds in strength, is much closer to truth.

In the case of heterocyclic aromatics and substituted benzenes, the electronegativity differences between different parts of the ring may dominate the chemical behaviour of aromatic ring bonds, which otherwise are equivalent.

Metallic bond
In a metallic bond, bonding electrons are delocalized over a lattice of atoms. By contrast, in ionic compounds, the locations of the binding electrons and their charges are static. The freely-moving or delocalization of bonding electrons leads to classical metallic properties such as shininess (surface light reflectivity), electrical and thermal conductivity, ductility, and high tensile strength.

Intermolecular bonding

There are four basic types of bonds that can be formed between two or more (otherwise non-associated) molecules, ions or atoms. Intermolecular forces cause molecules to be attracted or repulsed by each other. Often, these define some of the physical characteristics (such as the melting point) of a substance. A large difference in electronegativity between two bonded atoms will cause a permanent charge separation, or dipole, in a molecule or ion. Two or more molecules or ions with permanent dipoles can interact in dipole-dipole interactions. The bonding electrons in a molecule or ion will, on average, be closer to the more electronegative atom more frequently than the less electronegative

one, giving rise to partial charges on each atom, and causing electrostatic forces between molecules or ions. A hydrogen bond is effectively a strong example of a permanent dipole. The large difference in electronegativities between hydrogen and any of fluorine, nitrogen and oxygen, coupled with their lone pairs of electrons cause strong electrostatic forces between molecules. Hydrogen bonds are responsible for the high boiling points of water and ammonia with respect to their heavier analogues. The London dispersion force arises due to instantaneous dipoles in neighbouring atoms. As the negative charge of the electron is not uniform around the whole atom, there is always a charge imbalance. This small charge will induce a corresponding dipole in a nearby molecule; causing an attraction between the two. The electron then moves to another part of the electron cloud and the attraction is broken. A cationpi interaction occurs between the electron density of pi bonds above and below an aromatic ring and a cation.

Summary: electrons in chemical bonds

In the (unrealistic) limit of "pure" ionic bonding, electrons are perfectly localized on one of the two atoms in the bond. Such bonds can be understood by classical physics. The forces between the atoms are characterized by isotropic continuum electrostatic potentials. Their magnitude is in simple proportion to the charge difference.

Covalent bonds are better understood by valence bond theory or molecular orbital theory. The properties of the atoms involved can be understood using concepts such as oxidation number. The electron density within a bond is not assigned to individual atoms, but is instead delocalized between atoms. In valence bond theory, the two electrons on the two atoms are coupled together with the

bond strength depending on the overlap between them. In molecular orbital theory, the linear combination of atomic orbitals (LCAO) helps describe the delocalized molecular orbital structures and energies based on the atomic orbitals of the atoms they came from. Unlike pure ionic bonds, covalent bonds may have directed anisotropic properties. These may have their own names, such as sigma bond and pi bond.

In the general case, atoms form bonds that are intermediates between ionic and covalent, depending on the relative electronegativity of the atoms involved. This type of bond is sometimes called polar covalent.