Orbitals and Molecular Structure

Page 1 of 1
com
g.
ng
ye
.m
w
w
w
http://www.chem.ox.ac.uk/vrchemistry/pt/ptable.swf 2006/12/11
Foundations to Chemistry - adapted from "Chemistry, Matter and the Universe" Page 1 of 1
9. Molecular Orbitals and -- Jump to --
Molecular Structure
sp3 Hybrid Orbitals
Most compounds of second- and third-row nonmetals involve tetrahedral or
near- tetrahedral geometry around a central atom. We already have discussed
methane, CH , which has ideal tetrahedral H-C-H angles of 109.5 , ammonia,
NH , with H-N-H angles of 107 ; and water with an H-O-H angle of 105 .
Tetrahedral bonding geometry can be obtained by combining an s and three p
atomic orbitals of the central atom before bringing in other atoms, to produce a
set of four new orbitals called hybrid atomic orbitals, as at the right. These
hybrid orbitals can be represented by t , t , t , and t , and can be written
formally as
t =s+p +p +p
t =s+p -p -p
t = s -p +p -p
om
t = s -p -p +p
All four hybrid orbitals have an equal contribution from the spherical s orbital,
c
but they point in different directions because they have different contributions
g.
from p p and p The four hybrid orbitals extend out in the four directions of
ng
the vertices of a tetrahedron, or to four nonneighboring comers of a cube. The
signs of the p terms in the set of four equations above are, in effect, the
coordinates of each orbital The t orbital, for example, has its maximum
ye
electron probability in the -x, +y, -z direction, as can be seen to the right.
.m
Page 27 of 67
w
w
w
http://www.chem.ox.ac.uk/vrchemistry/orbitals/html/page26.htm 2006/12/11
Molecular Structure
sp3 Hybrid Orbitals
Most compounds of second- and third-row nonmetals involve tetrahedral or
near- tetrahedral geometry around a central atom. We already have discussed
methane, CH , which has ideal tetrahedral H-C-H angles of 109.5 , ammonia,
NH , with H-N-H angles of 107 ; and water with an H-O-H angle of 105 .
Tetrahedral bonding geometry can be obtained by combining an s and three p
atomic orbitals of the central atom before bringing in other atoms, to produce a
set of four new orbitals called hybrid atomic orbitals, as at the right. These
hybrid orbitals can be represented by t , t , t , and t , and can be written
formally as
t =s+p +p +p
t =s+p -p -p
t = s -p +p -p
om
t = s -p -p +p
All four hybrid orbitals have an equal contribution from the spherical s orbital,
c
but they point in different directions because they have different contributions
g.
from p p and p The four hybrid orbitals extend out in the four directions of
ng
the vertices of a tetrahedron, or to four nonneighboring comers of a cube. The
signs of the p terms in the set of four equations above are, in effect, the
coordinates of each orbital The t orbital, for example, has its maximum
ye
electron probability in the -x, +y, -z direction, as can be seen to the right.
.m
Page 27 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
These four tetrahedral hybrid atomic orbitals are less stable than the s and
three p orbitals from which they came, because a small amount of energy is
required to bring the s-orbital energy up to the energy of p before they can be
hybridisied. This energy is regained several times over whn bonds are formed
between these hybrid orbitals and orbitals from other atoms, so the mixing is
possible. The four tetrahedral orbitals are called sp hybrid atomic orbitals.
Bonding in methane is illustrated at the right. Each of the four sp hybrid
orbitals can combine with a hydrogen 1s atomic orbital to form a localised
bonding and antibonding pair of MO's. The antibonding MO's are of no
importance for methane because thwey are never occupied. But when one of
the bonding orbitals is filled with a pair of electrons, a bond is formed between
C and H. The sp hybridisation leads to the observed molecular geometry with
bond angles of 109.5. Formation of four such bonds uses all of the 1s orbitals
of the four hydrogen atoms, and the s, p , p and p orbitals from carbon.
om
Filling the bonding orbitals requires all four H electrons and all four second-
shell electrons from C. The 1s orbital of carbon and its electron pair are not
involved in the bonding process.
c
g.
ng
ye
.m
Page 28 of 67
w
w
w
http://www.chem.ox.ac.uk/vrchemistry/orbitals/html/page26a.htm 2006/12/11
Molecular Structure
sp3 Hybrid Orbitals
om
c
g.
ng
ye
.m
Page 28 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
om
c
g.
ng
ye
.m
Page 28 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
The Sp hybridization model also can be used for molecules involving N and O,
with lone electron pairs filling some of the Sp orbitals. Thus an improved
picture of water (below) employs two of the Sp orbitals in bonds with hydrogen,
and the other two for the two lone electron pairs on 0. This Sp model predicts
a tetrahedral H-0-H bond angle of 109.51. The smaller observed angle of 105
can be explained by the strong repulsion generated by the lone pairs, which are
closer to the oxygen atom and to each other than are the bonding electron
pairs.
c om
g.
ng
ye
Page 29 of 67
.m
w
w
w
Foundations to Chemistry - Chapter 11 - adapted from "Chemistry, Matter and the Un... Page 1 of 1
Molecular Structure
sp3 Hybrid Orbitals
The great simplification in this localized hybrid picture is
that each C-H bond involves only one hybrid orbital
from carbon, and what the other three Sp orbitals are
doing is irrelevant. Bonds can be considered one at a
time, and it is not necessary to throw all five atoms into
one great mathematical pot. Consequently calculations
of electron density and energy are greatly simplified.
The same Sp hybridization can be used for ethane, H
C-CH and for a great many other carbon
compounds. In ethane, shown at the left, three of the
four Sp3 hybrid atomic orbitals on each carbon are
combined with atomic orbitals of hydrogen, as in
methane, and the fourth is combined with one sp3 from
the other carbon atom. The sp3 hybrid orbitals extend
om
out farther from the nucleus than the is orbitals of
hydrogen do, so a C-C bond is longer than a C-H bond:
1.54 Å versus 1.09 Å. Bond angles throughout the
c
molecule still have tetrahedral values of 109.5 . The
two ends of the molecule can rotate freely around the
g.
C-C bond, but the most stable arrangement of
hydrogen atoms by a small amount of energy is that
ng
shown at the lower left. The hydrogen atoms are
"staggered" so that the hydrogen atoms on one carbon
ye
atom are as far as possible from the hydrogens on the

other carbon atom.
.m
Page 30 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
The sp3 hybridization model also can be used for
molecules involving N and 0, with lone electron pairs
filling some of the sp3 orbitals. Thus an improved
picture of water (below) employs two of the sp3 orbitals
in bonds with hydrogen, and the other two for the two
lone electron pairs on 0. This sp3 model predicts a
tetrahedral H-0-H bond angle of 109.51. The smaller
observed angle of 105 can be explained by the strong
repulsion generated by the lone pairs, which are closer
to the oxygen atom and to each other than are the
bonding electron pairs.
c om
g.
ng
ye
.m
Page 31 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
c om
g.
ng
ye
.m
Page 31 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
c om
g.
ng
ye
.m
Page 31 of 67
w
w
w
Molecular Structure
sp3 Hybrid Orbitals
c om
g.
ng
ye
.m
Page 31 of 67
w
w
w
Molecular Structure
Double Bonds and sp2 Hybridisation
Ethylene, H C-CH , is typical of carbon compounds that have double bonds
between atoms. The carbon-carbon bond length in ethylene is 1.34Å,
compared to 1.54Å in ethane, and the bond energy, or energy required to pull
the carbon atoms apart, is 147 kcal mole , rather than 83 kcal mole for
ethane. Furthermore, the carbon-carbon double bond is rigid. No rotation is
possible around the bond, and the two carbon atoms and four hydrogen atoms
all are constrained to lie in one plane. The H-C-H bond angle at either end of
the molecule is 117 . How can MO theory account for these characteristics of
ethylene? Ethylene has 12 outer-shell atomic orbitals involved in bonding: one
s and three p orbitals from each carbon, and a Is from each of the four
hydrogens. It also has 12 outer-shell electrons to place in MO's: four each from
the carbons and one each from the hydrogens. The Is carbon orbitals are filled
with electron pairs, do not overlap appreciably, and play no part in bonding.
One solution to the bonding problem would be to begin with sp3 hybrid orbitals
om
around the carbons, and to assume that each carbon atom shares two such
tetrahedral orbitals with the other, as shown at the lower right. This is unlikely,
because of the severely bent bonds that would result between carbons. It is
c
also wrong, because it predicts a H-C-H bond angle of 109.5 instead of the
g.
observed 117 .
ng
ye
.m
Page 32 of 67
w
w
w
Molecular Structure
Ethylene, H C-CH , is typical of carbon compounds that have double bonds
between atoms. The carbon-carbon bond length in ethylene is 1.34Å,
compared to 1.54Å in ethane, and the bond energy, or energy required to pull
the carbon atoms apart, is 147 kcal mole , rather than 83 kcal mole for
ethane. Furthermore, the carbon-carbon double bond is rigid. No rotation is
possible around the bond, and the two carbon atoms and four hydrogen atoms
all are constrained to lie in one plane. The H-C-H bond angle at either end of
the molecule is 117 . How can MO theory account for these characteristics of
ethylene? Ethylene has 12 outer-shell atomic orbitals involved in bonding: one
s and three p orbitals from each carbon, and a Is from each of the four
hydrogens. It also has 12 outer-shell electrons to place in MO's: four each from
the carbons and one each from the hydrogens. The Is carbon orbitals are filled
with electron pairs, do not overlap appreciably, and play no part in bonding.
One solution to the bonding problem would be to begin with sp3 hybrid orbitals
om
around the carbons, and to assume that each carbon atom shares two such
tetrahedral orbitals with the other, as shown at the lower right. This is unlikely,
because of the severely bent bonds that would result between carbons. It is
c
also wrong, because it predicts a H-C-H bond angle of 109.5 instead of the
g.
observed 117 .
ng
ye
.m
Page 32 of 67
w
w
w
Molecular Structure
Bond angles close to 120 suggest three equal orbitals
in a plane. This geometry can be obtained by combining
the s. orbital and two of the three p orbitals of each
carbon into a set of three Sp2 hybrid atomic orbitals.
The third, unhybridized p orbital extends vertically
above and below the plane of the page. In ethylene, two
of the three Sp2 orbitals on each carbon are combined
with hydrogen Is orbitals, and the third is involved in the
bond with the other carbon. These all are a- bonds
because they are symmetrical about the individual bond
axes. This σ framework of the ethylene molecule uses
ten of the twelve available bonding electrons, and all of
the outer-shell atomic orbitals except one unhybridized
2p, orbital on each carbon.
c om
g.
ng
ye
Page 33 of 67
.m
w
w
w
Molecular Structure
The second half of the double bond in ethylene arises from a combination of
these last two p orbitals into a molecular orbital with z lobes of density of
opposite sign above and below the plane of the molecule. The double bond is
shorter than a single bond because the p. orbitals must come closer together
before they overlap enough to bond. The orbital also forces the molecule to
be planar. Twisting about a bond axis is harmless to a symmetrical σ, bond,
but breaks a π bond by pulling the p orbitals out of alignment. To twist one end
of the ethylene molecule 90 relative to the other, one would have to supply
energy equal to the difference between a C-C double bond and a single bond,
or 147 - 83 = 64 kcal mole . The ideal H-C-H bond angle of 120 at each end
of the ethylene molecule is decreased to 117 by electron-pair repulsion
between the double bond and the two C-H single bonds. Double bonds are of
great importance in biological molecules, both because they help make
om
proteins and other molecules rigid and because of their unique ability to absorb
light. We will come back to the structural rigidity aspects in the chapter on
proteins, and to their light-absorbing properties in the postscript to this chapter.
c
g.
ng
ye
Page 34 of 67
.m
w
w
w
Molecular Structure
The second half of the double bond in ethylene arises from a combination of
these last two p orbitals into a molecular orbital with z lobes of density of
opposite sign above and below the plane of the molecule. The double bond is
shorter than a single bond because the p. orbitals must come closer together
before they overlap enough to bond. The orbital also forces the molecule to
be planar. Twisting about a bond axis is harmless to a symmetrical σ, bond,
but breaks a π bond by pulling the p orbitals out of alignment. To twist one end
of the ethylene molecule 90 relative to the other, one would have to supply
energy equal to the difference between a C-C double bond and a single bond,
or 147 - 83 = 64 kcal mole . The ideal H-C-H bond angle of 120 at each end
of the ethylene molecule is decreased to 117 by electron-pair repulsion
between the double bond and the two C-H single bonds. Double bonds are of
great importance in biological molecules, both because they help make
om
proteins and other molecules rigid and because of their unique ability to absorb
light. We will come back to the structural rigidity aspects in the chapter on
proteins, and to their light-absorbing properties in the postscript to this chapter.
c
g.
ng
ye
Page 34 of 67
.m
w
w
w
Molecular Structure
Triple bonds and sp hybridisation
In a relatively small number of compounds, carbon is connected to another
atom by a triple bond involving three electron pairs. This type of bond can be
built from sp hybrid orbitals involving one s and one p orbital on each carbon
atom, as shown at the bottom of the page. Two sp hybrid atomic orbitals
extend out from an atom 180 apart, and the two remaining unhybridized p
orbitals are at right angles to these and to one another. In acetylene, H-C=C-H,
each of the two carbon atoms uses one sp hybrid orbital in a C-H bond and the
other in the bond between carbons. Three electron pairs are employed in
holding this a-bonded framework together.
The remaining two thirds of the triple bond involves the p orbitals. If the C-C
bond direction is chosen as the z axis, then the two p. orbitals on carbon
combine into one π MO, and the two p , orbitals combine into another. This
means that the carbon atoms are held together by three electron pairs, one in
om
a σ bond and two in π bonds. The and MO's taken together from a
symmetrical barrel of electron density around the carbon-carbon bond.
c
g.
ng
ye
Page 35 of 67
.m
w
w
w
Molecular Structure
Triple Bonds and sp Hybridisation
The acetylene molecule is linear, with all four atoms in a straight line. The C-H
bond lengths are little different from those of other molecules, but the three
electron pairs in the triple bond pull the carbon atoms together until they are
only 1.21 Å apart, compared with 1.34 Å for a double bond and 1.54 Å for a
single bond. If a nitrogen atom replaces one carbon, a triple bond is still
possible, but then the C-H with an electron pair bond is replaced by N:, with its
lone electron pair, and the result is HCN (hydrogen cyanide), which is shown at
the right. If the other carbon atom also is replaced by N, the result is the triply
bonded N~ molecule. This is the end of the road for bonds between most
atoms. Quadruple bonds involving s and p orbitals are geometrically
impossible. An absolute requirement for bonding is that the AO's from the two
atoms overlap, and as the bond order increases from single to double to triple,
the atoms have to be pushed closer together to achieve this overlap. No matter
how the s and three p orbitals are hybridized, the only way to make all four
om
orbitals overlap with the corresponding four from another atom is to push the
atoms together until their nuclear centers coincide-an impossible thing to do.
Hence, quadruply bonded C gas molecules, sharing all four bonding electrons
c
on one C with a single partner, are not found. This is one reason for the
observed dramatic difference in properties of the pure elements, between solid
g.
diamond and N , O , and F gases. The C molecule can exist, but only with
incomplete electron-sharing. This makes
ng
C very reactive and stable only at high temperatures.
ye
.m
Page 36 of 67
w
w
w
Molecular Structure
Triple Bonds and sp Hybridisation
c om
g.
ng
ye
.m
Page 38 of 67
w
w
w
Molecular Structure
Aromaticity: Delocalisation and resonance
What we have just gone through has been the outline of a very successful
theory of molecular structure and bonding. What has not been covered is the
quantitative calculation of shapes and energies of molecular orbitals that
makes MO theory even more attractive. We began by abandoning the concept
of a "bond" and looking at the entire molecule at once. It is perhaps fortunate
for our computational sanity that such a procedure usually is excessive with
larger molecules, and that the approximation of localized molecular orbitals
and two-atom bonds can be used instead. Adding the concepts of hybridization
and single, double, and triple bonds provides the framework of a theory that
can explain most molecules. One important class of molecules that cannot be
explained in terms of two-atom bonds is the organic aromatic molecules,
mentioned briefly in Chapter 4. Benzene, C H , is the most familiar example.
It has six carbon atoms in a regular hexagonal ring, with all carbon-carbon
bonds 1.39 Å long, which is intermediate between single and double bond
om
lengths. Each carbon has one C-H bond of normal length. The skeleton of
benzene is shown.
c
g.
ng
ye
.m
Page 39 of 67
w
w
w
Molecular Structure
As soon as we try to make a localized MO model of benzene, we run into
trouble. The planar hexagonal geometry of the molecule, with 120 bond
angles, suggests sp2 hybridization around the carbons, with one spl orbital
from each C pointed toward an H, and the other two directed toward the
neighboring carbon atoms in the ring. This skeleton of σ bonds uses 24 of the
30 bonding electrons (6 X 4 from carbons plus 6 x 1 from hydrogens), and all
of the outer orbitals except the six p orbitals perpendicular to the plane of the
hexagon. This σ framework is shown. What should be done with the six
unused electrons and six remaining p orbitals? These are shown in
perspective at the bottom left. Adjacent p orbitals could be combined in pairs
around the ring to make every other carbon-carbon bond a double bond. There
are two ways of doing this, represented schematically below. These are known
as the Kekule structures after the man who first proposed them, but they
cannot be correct because we know that all of the carbon-carbon bonds are
om
the same length. A somewhat less plausible way of pairing the p orbitals would
be to connect two across the ring, and then pair the remaining two at either
side, as in the three Dewar structures shown below the Kekule rings.
c
g.
ng
ye
.m
Page 40 of 67
w
w
w
Molecular Structure
om
c
g.
ng
ye
.m
Page 40 of 67
w
w
w
Molecular Structure
om
c
g.
ng
ye
.m
Page 40 of 67
w
w
w
Molecular Structure
om
c
g.
ng
ye
.m
Page 40 of 67
w
w
w
Molecular Structure
All five of these Kekule and Dewar structures, considered individually, are
wrong. There is no way to write the correct benzene structure as a set of single
and double bonds, so the localized bond approximation, which has proven so
useful for methane and other multi-atom molecules, breaks down. We must
retreat a little way from localized bonds toward the whole-molecule approach
again, at least where p electrons are concerned. We can combine the six p
orbitals around the benzene ring according to the rules of MO theory, and
produce the six full-ring MO's sketched above. In the lowest-energy orbital,
all six p AO's are combined with the same sign to produce two rings of
electron density above and below the plane of the benzene skeleton. There is
zero electron probability in this plane because the original p orbitals had zero
probability there. Like the two lobes of density in the p orbitals from which they
came, the two "doughnuts" of probability in the , MO have opposite wave-
om
function signs. The next most stable MO's, and , have the same energy
and the same shape, with one horizontal or vertical plane of zero probability
perpendicular to the benzene ring. Two antibonding orbitals with the same
energy, and
c
, each have two such zero-probability nodes at right
g.
angles, and the least stable antibonding orbital, , has three such nodes.
ng
ye
.m
Page 41 of 62
w
w
w
Molecular Structure
om
energy, and
c
g.
ng
ye
.m
Page 41 of 62
w
w
w
Molecular Structure
om
energy, and
c
g.
ng
ye
.m
Page 41 of 62
w
w
w
Molecular Structure
The energy-level diagram for these six MO's appears at the right. As we have
seen consistently in other AO's and MO's, the general principle holds that,
other things being equal, the more nodes of zero probability in an orbital, the
higher its energy. Six p atomic orbitals are combined to form six molecular
orbitals-three bonding and three antibonding. The six electrons not used in the
o, framework of the benzene molecule are used to fill the three bonding MO's,
and the antibonding orbitals are unused. The benzene ring therefore has three
more bonds in addition to its σ-bonded skeleton, but these three bonds are
spread around the entire ring rather than being localized between pairs of
carbon atoms, as the Kekule or Dewar models would predict. All of the carbon-
carbon bonds in the ring are intermediate between "single" and "double," and
their observed bond length verifies this.
c om
g.
ng
ye
.m
Page 42 of 62
w
w
w
Molecular Structure
There is another way of looking at bonding in benzene that preserves the
language of single and double bonds. This is to say that an of the Keku16 and
Dewar structures are partially correct, but that no one of them alone is a
sufficiently good description of reality. The real benzene molecule in some way
is a combination of all of them, like a mule is a combination of a horse and a
donkey. Unfortunately, the term "resonance" has become associated with this
viewpoint, and these partially correct structures are called resonance structures.
This term gives the quite erroneous idea of a flipping back and forth among the
several structures. The benzene molecule contains features of all five
resonance structures, but it no more flips back and forth between them, than a
mule "resonates" before your eyes from horse to donkey and back again.
Nevertheless, the term resonance is so firmly embedded in the language of
chemistry that we shall use it too. The 40 kcal mole of extra stability of the
molecules over that of a KekuIe structure is called the resonance energy of the
om
benzene molecules.
c
g.
ng
ye
Page 43 of 67
.m
w
w
w
Molecular Structure
Resonance structures provide a handy way of deciding how far delocalization
extends in a molecule. A set of resonance structures for a molecule must have
the atomic nuclei in the same places, and can differ only in the placement of
electrons and hence of bonds and charges. When all possible resonance
structures have been written for a molecule that cannot be described
adequately by simple single and double bonds, then all atoms that are
connected by double bonds in at least one of the resonance structures are
involved in the delocalized electron system. For benzene these are the six
carbon atoms, and the hydrogens play no part in delocalization. Delocalization
in carbon compounds almost always involves the combination of a set of p
orbitals perpendicular to the plane of a molecular skeleton connected by σ-
bonds. The double bonds do not have to be alternating around a closed ring for
delocalization to occur. In the butadiene molecule shownon the next page, four
carbon atoms are connected in a linear chain with two double bonds. Structure
om
(b) is the one usually thought of for butadiene, but it cannot be completely right
because all ten atoms in the real molecule lie in a plane, and this would not
necessarily be true if the central carbon-carbon bond were a single bond.
c
g.
ng
ye
Page 44 of 67
.m
w
w
w
Molecular Structure
After making the skeleton of σ- bonds using sp2 hybridization around carbons,
four electrons and four p orbitals in butadiene remain unused, and the p
orbitals are arranged as in the perspective drawing (a) at the upper left. As in
benzene, these p orbitals can be combined in several ways to produce various
resonance structures for the molecule. Four resonance structures are shown in
drawings (b) - (e) at left. All four carbon atoms are linked in a delocalized
electron system. Compounds with alternating single and double bonds, in
which p-electron delocalization can occur, are called conjugated molecules.
Whether linear or in closed rings, conjugated molecules somewhat larger than
butadiene or benzene have the useful property of absorbing visible light, as we
shall see in the postscript. Linear conjugated molecules are used in the
photoreceptors of the eye, and both linear and aromatic conjugated molecules
are put to work in trapping light in photosynthesis.
c om
g.
ng
ye
.m
Page 45 of 67
w
w
w
Molecular Structure
After making the skeleton of σ- bonds using sp2 hybridization around carbons,
four electrons and four p orbitals in butadiene remain unused, and the p
orbitals are arranged as in the perspective drawing (a) at the upper left. As in
benzene, these p orbitals can be combined in several ways to produce various
resonance structures for the molecule. Four resonance structures are shown in
drawings (b) - (e) at left. All four carbon atoms are linked in a delocalized
electron system. Compounds with alternating single and double bonds, in
which p-electron delocalization can occur, are called conjugated molecules.
Whether linear or in closed rings, conjugated molecules somewhat larger than
butadiene or benzene have the useful property of absorbing visible light, as we
shall see in the postscript. Linear conjugated molecules are used in the
photoreceptors of the eye, and both linear and aromatic conjugated molecules
are put to work in trapping light in photosynthesis.
c om
g.
ng
ye
.m
Page 45 of 67
w
w
w
Molecular Structure
Delocalization has appeared several times in previous
chapters, but only now can we give it an interpretation
in terms of molecular orbitals. The benzene molecule
was introduced in Chapter 4, and the carbonate and
nitrate ions in Chapter 5. The various Lewis dot models
for CO , which assigned single- or double-bond
character to different combinations of the three C-0
bonds, were resonance structures for the carbonate ion,
differing only in the positioning of electrons between
atoms. The phosphate, sulfate, and perchlorate ions
discussed in Chapter 6 also were examples of
delocalization. In all of these examples, delocalization
brought extra stability to the ion, and it is a good
om
practical rule of thumb that the more resonance
structures one can draw for a delocalized ion or
molecule, the more stability this delocalization creates.
c
g.
ng
ye
Page 46 of 67
.m
w
w
w
Molecular Structure
Molecular orbital picture of bonds: a summary
In MO theory a bond is formed when atomic orbitals of similar energy and
symmetry combine to form at least one molecular orbital of lower energy than
that of the isolated AO's, and when that bonding MO then is filled by a pair of
electrons. In principle, all bonds extend over the entire molecule, but in practice
it is usually possible to consider only two atoms at a time, and to think of the
bond between them as being independent of all other bonds in the molecule.
This localized-bond picture sometimes fails us, especially when p orbitals are
involved in delocalization along chains or rings of carbon atoms. When this
occurs, the molecular skeleton can be treated as a set of a- bonds, and the p
orbitals can be treated separately. The filled inner shells in atoms can be
ignored in bonding, and only the outer orbitals and outer-shell electrons need
be considered. In localized, two-atom bonds, the s and three p atomic orbitals
usually are not the best starting points in bonding. All four orbitals can be
hybridized, before they are combined with orbitals from other atoms, to produce
om
a set of four identical sp3 hybrid orbitals pointing in tetrahedral directions.
Alternatively, the s and two of the p orbitals can be hybridized into three Sp2
orbitals 120 apart in a plane; or the s and one p can be combined into two sp
c
orbitals pointing in opposite directions from the atom. The best hybridization to
g.
use depends on the actual geometry of the molecule, and on the presence of
double or triple bonds.
ng
ye
Page 47 of 67
.m
w
w
w
Molecular Structure
Molecular orbital picture of bonds: a summary
Bonding orbitals in MO theory always concentrate an excess of electron density
between the atoms being bonded, and in this regard the MO theory is no
different from the old qualitative electron-pair ideas of a bond. But only MO
theory recognizes that electron pairs can tear a molecule apart as well, if they
are placed in antibonding orbitals. The essential factor in determining bonding is
the net excess of bonding electrons over antibonding electrons. If these
bonding and antibonding electrons counterbalance one another, then the
molecule will not form, as we saw for He , Be , and Ne . Nothing in MO theory
contradicts the simpler electron-pair theory, or we would have grave doubts
about its validity. But even more, MO theory explains molecular properties
about which the simpler theory has nothing to say-for example, the magnetic
behavior of the O molecule with its two unpaired electrons, and the planarity of
molecules with double bonds. This chapter has been a pictorial and qualitative
introduction to molecular orbital theory, but the theory also has a mathematical
om
and quantitative side that permits the calculation of energy levels and of
ionization energies, spectra, and reactivities of molecules.
c
g.
ng
ye
Page 48 of 67
.m
w
w
w
Molecular Structure
Postscript: Delocalisation and color
Aromatic compounds are carbon-framework molecules
in which the carbon skeleton is held together in flat
rings by o- bonds, and the carbon p orbitals
perpendicular to the rings are involved in extensive
delocalized electron systems. Benzene is the simplest
such molecule, but many rings can be fused together in
larger molecules. Naphthalene, C H , has two fused
rings; anthracene, C H has three, and many larger
molecules exist (see right). Replacing the peripheral
hydrogens by other chemical groups gives rise to a rich
and varied branch of organic chemistry, which includes
many biologically important molecules, flavorings,
dyestuffs, light receptors, and carcinogenic (cancer-
om
producing) agents.
c
g.
ng
ye
.m
Page 49 of 67
w
w
w
Molecular Structure
A common property of aromatic molecules is their ability to absorb
electromagnetic radiation in the near ultraviolet or even in the visible range,
thereby making the molecules brightly colored. The effect of combining p
orbitals in benzene into a set of delocalized MO's is to split the energy of the
individual p orbitals into four closely spaced energy levels, which were
diagramed previously. In benzene, the three bonding orbitals are filled and the
antibonding orbitals are empty. If the right frequency of radiation is supplied, a
benzene molecule can absorb it and promote one or more electrons from
bonding to antibonding orbitals. The gap between levels is a measure of the
energy needed to make the transition from the ground state (lowest energy) to
an excited electronic state. An excited molecule can emit this energy later as a
photon of radiation, and drop back to the ground state. Nonaromatic molecules
also can be electronically excited, but larger amounts of energy are required,
and this means that absorption and emission take place farther into the
om
ultraviolet. If enough energy is supplied, the σ- single bonds can be broken and
the molecules destroyed. The special property of aromatic molecules is that
their π− orbital energy levels are closely spaced , which leads to absorption in
c
the lower-energy, longer-wavelength region. g.
ng
ye
Page 50 of 67
.m
w
w
w
Molecular Structure
Delocalization leads to a lowering of energy levels and narrowing of the
spacings between levels; and the larger the delocalized system, the greater
this effect. This can be seen in the series of aromatic molecules compared at
the bottom of the opposite page. Benzene has six atoms in its delocalized π-
electron system, and the spacings between the π-orbital energy levels are
such that it absorbs energy at a set of wavelengths in the ultraviolet region,
centered around 2550 Å. The visible wavelengths pass through the molecule
untouched, so benzene is colorless to our eyes. So are naphthalene and
anthracene, which have 10 and 14 atoms in the delocalized system, although
the larger rings shift the absorption to longer wavelengths or lower energies:
3150 Å and 3800 Å. In contrast, delocalization in naphthacene is so extensive
that the splitting between ir energy levels has narrowed to the point where blue
light around 4800 Å is absorbed. With the blue light absorbed, the remaining
visible wavelengths make naphthacene appear orange, the complement of
om
blue. In pentacene, which has five rings, absorption is shifted down to even
lower energies. Pentacene removes yellow light around 5800 Å and therefore
appears indigo. This "eyeball spectroscopy" is surprisingly informative in
c
revealing what aromatic molecules are doing. The visible spectrum is shown at
g.
the right, with colors recorded as a function of wavelength from the ultraviolet
to the infrared. If any of these wavelengths is absorbed by a molecule, the
ng
remaining wavelengths give the molecule the complementary color. Removal
of green wavelengths around 5300 Å makes a molecule appear purple. If the
molecule absorbs red light at around 6800 Å, we will see it as blue-green. By
ye
looking at what is left of the visible spectrum after absorption, we can decide
approximately what visible wavelengths the compound is absorbing.
.m
Page 51 of 67
w
w
w
Molecular Structure
Any attached side group on the ring that increases the number of atoms in the
delocalized system will shift the electronic absorption toward lower energy and
longer wavelengths. Early industrial dyestuff chemists knew by experience that
some chemical groups such as -OH and -NH would shift the colors of aromatic
molecules down the series yellow-orange-red-purple-blue-green, the
complement of the absorbed visible spectrum, violet-blue-green-yellow-orange-
red, before they understood the relationship among color, frequency, and
energy. Adding an -OH group to benzene to produce phenol, C H OH, shifts
the center of the absorption band slightly, from 2550 Å to 2700 Å, since the
oxygen in the -OH group is rich in electrons. Phenol is an acid, and can
dissociate and lose the proton of the -OH to form the phenolate ion:
C H OH --> C H O + H+
phenol phenolate ion
c om
g.
ng
ye
Page 52 of 67
.m
w
w
w
Molecular Structure
In the phenolate ion the oxygen actually becomes part of the delocalized
system and enlarges it from six atoms to seven. You can see this by comparing
the various resonance structures for phenol and the phenolate ion at the left.
Only benzenelike resonance structures are possible for phenol, since the -OH
group really is not included in the delocalized system. The phenolate ion has
resonance structures in which the oxygen has three lone pairs and a negative
charge, and is attached to the ring by a single bond. But other resonance
structures can be drawn in which one of the three lone pairs is shifted into a
C=0 double bond, and the negative charge shows up at different positions on
the ring. These resonance structures tell us that in the ion the oxygen is part of
the general seven-atom delocalized system. With greater delocalization, the
spacings between π-orbital energy levels are decreased, and the electronic
absorption band shifts from 2700 Å to 2870 Å. We cannot see this change
because our eyes are insensitive to the ultraviolet, but if all the wavelengths
om
were doubled, benzene would be red, phenol would be purple, and the
phenolate ion would be blue-violet. Phenol then would bean acid- base
indicator, revealing the acidity of its environment by its color. If added in small
c
amounts to a solution, it would appear purple in acid, where its own dissociation
g.
was repressed by a plentiful H+ supply, and blue-violet in base, where most of it
had dissociated to the phenolate ion.
ng
ye
Page 53 of 67
.m
w
w
w
Molecular Structure
Phenol is not a usable acid-base indicator because it absorbs in the wrong part
of the spectrum, but the same principles explain why slightly larger aromatic
molecules make good indicators. Alizarin, shown at the top of the next page, is
a derivative of anthracene. The two double-bonded oxygens on the center ring
enlarge the delocalized system from 14 atoms to 16, and shift the center of
absorption from 3800 Å in the ultraviolet to 4300 Å in the indigo part of the
visible spectrum. The unabsorbed wavelengths make alizarin yellow. The two -
OH groups on the outer ring do not participate in the delocalized system until
they dissociate, as they do in basic solutions in which III ions are scarce. When
this happens, the two hydroxyl oxygens become just as much a part of the
delocalization as the original double-bonded oxygens. You can see this by
drawing other resonance structures that give the hydroxyl oxygens the double
bonds. This enlargement shifts the main absorption to around 4800 Å in the
blue re Delocalization of phenol in acid (gray tint) and phenolate ion in base
om
(color tint) gion, and makes the solution of ions orange. Alizarin is one of the
standard acid-base indicators, turning Yellow in acid and orange in base.
Phenolphthalein, which is colorless in acid and deep red in base, and methyl
c
violet, which is yellow in acid and violet in base, are other examples of
g.
aromatic acid-base indicators.
ng
ye
.m
Page 54 of 67
w
w
w
Molecular Structure
Linear conjugated molecules with alternating single and double bonds also will
absorb light if they are long enough. Carotenoids, which are "super butadienes"
with 22 carbon atoms connected by alternating single and double bonds, are
used as antennae by green plants to trap light and transfer the energy to
chlorophyll for use in chemical syntheses. They are bright yellow-orange
because they have evolved over the past 3.5 billion years to absorb light in the
5000 Å wavelength region (blue-green), which is the most intense part of solar
radiation. Living organisms use aromatic and straight-chain conjugated
molecules to trap light energy, to transfer this energy from one molecule to
another, and to recognize the presence of light so they can grow toward it, turn
toward it, or use it for information gathering through vision. The radiation that
reaches the surface of our planet covers a relatively narrow range. Ozone, O
in the upper layers of the atmosphere absorbs almost all wavelengths shorter
than 2900 Å, and water vapor absorbs much of the infrared. Little infrared
om
radiation longer than 13,000 Å remains by the time light reaches the surface of
the Earth, and only five meters below the surface of the ocean all radiation
longer than 8000 Å has been absorbed. The most intense radiation from the
c
sun occurs in the blue-green region, around 5000 Å, the region for which the
carotenes have evolved to absorb light.
g.
ng
ye
Page 55 of 67
.m
w
w
w
Molecular Structure
The loss of the infrared is of no consequence, because these wavelengths
contain so little energy per photon that they are not very good as energy
sources. At the short wavelength end of the solar spectrum, it is fortunate for us
that everything shorter than 2900 Å is cut off by the ozone layer, be cause
these "hard ultraviolet" photons are energetic enough to break the C-C and C-N
single bonds that hold proteins and other biological macromolecules together.
The energy of a C-C single bond, 83 kcal mole , corresponds to a wavelength
of 3500 Å. These and shorter wavelengths are potentially lethal, which is why
ultraviolet lamps can be used to kill bacteria and other microorganisms. Life
evolved in the oceans, bathed in a "window" of electromagnetic radiation from
about 2900 Å to 8000 Å, with maximum abundance around 5000 Å. It is no
accident that living creatures developed means of using this radiation as an
energy source, and as a means of sensing the environment through vision. The
molecules that absorb energy in this wavelength range are the aromatic and
om
linear conjugated molecules with delocalized double bonds. We will see in
subsequent chapters how the chlorophylls and carotenoids in photosynthesis,
and retinal in vision, all use the light-absorbing properties of delocalized π
c
molecular orbitals. g.
ng
ye
Page 56 of 67
.m
w
w
w
Molecular Structure
Questions
1. When atomic orbitals are combined into molecular orbitals, how does the
number of MO's obtained compare with the original number of AO's?
2. For a multiatorn molecule, what approximation are we using when we

combine atomic orbitals from atoms two at a time in forming bonds between
pairs of atoms? Why is this approximation useful? Give an example of a
molecule for which this approximation is valid, and another for which it breaks
down.
3. What is the distinction between bonding and antibonding MO's? How is it that
molecules such as N and F can have antibonding orbitals that are lower in
energy than some bonding orbitals?
4. How many electrons can each MO hold? What is the relationship between
om
the spins of electrons occupying the same MO? How does this compare with
the occupancy of AO's by electrons in isolated atoms?
c
5. In the hydrogenlike diatomic molecules ,H , , and He , why do the
g.
first two electrons increase the strength of the bond, and the third and fourth
electrons weaken the bond? What is the bond order in each of the above
ng
molecules or molecule-ions?
6. Compare the theoretical predictions in Question 5 with the observed bond

ye
lengths and bond energies. Does the bond length increase, or decrease, with
increasing bond order? Why?
.m
7. How do filled bonding MO's tend to hold the two bonded atomic nuclei
together? How do filled antibonding MO's tend to pull them apart? Explain in
w
terms of electron probability distributions.

w
8. What are the requirements in terms of location, energy, and symmetry of two
atomic orbitals if they are to be combined into molecular orbitals?
w
Page 57 of 67
Molecular Structure
Questions
9. What is meant by σ and π symmetry in molecular orbitals? How is this
nomenclature an obvious extension of the s and p notation for atomic orbitals?
Explain in terms of 180 rotations and the signs of the wave functions.
10. How is the bond energy of an electron-pair bond related relative energies of
the bonding and antibonding MO's and the AO's from which they were derived?
Explain with a diagram. If the energy difference between the AO's and the
bonding MO in H is x kcal mole , what is the bond energy of H ?
11. What is the relative order of increasing energies for the six MO's derived
from the six outer p AO's on tw o atoms in a diatomic molecule? How does this
energy sequence account for the observed bond orders in the diatomic
molecules obtained from second-row elements?
om
12. For which of the second-row elements do diatomic molecules not exist?
Why, in terms of MO theory? For which of these elements do diatomic
molecules occur only at high temperatures? What is the their state at 298K, and
c
why? For which of these elements is the diatomic molecule the stable form at
room temperature?
g.
ng
13. Which of the diatomic molecules of the second-row elements have unpaired
electrons? How many unpaired electrons do they have? Why are these
electrons not paired in the same orbital? How does the Lewis electron-dot
ye
model account for these unpaired electrons?
Page 58 of 67
.m
w
w
w
Molecular Structure
Questions
14. How do the observed bond lengths and bond energies of the second-row
diatomic molecules correlate with the predicted bond order?
15. When AO's of different kinds of atoms are being combined to build an MO,
what important energy criterion helps to decide which AO's on the two atoms
will interact9 What symmetry considerations are important? Illustrate with the
HF molecule.
16. Draw the Lewis electron-dot model for the HF molecule. The F atom should
be represented as having one bond to H, and three lone electron pairs. In MO
theory, what orbitals do these three electron pairs occupy? Which fluorine AO is
involved in the H-F bond?
17. To which MO does the fluorine 2p AO make the greatest contribution, the
om
bonding MO or the antibonding? What does this imply in terms of the location of
the bonding electron pair and the polarity of the bond? How is this related to the
relative electronegativities of H and F?
c
g.
18. How are the energy levels of the hydrogen is and fluorine 2p atomic orbitals
related to the first ionization energies of H and F? (The correlation is
ng
approximate, but useful.)
19. In the limit of completely ionic bonding between two atoms of very high and
ye
very low electronegativities, how would the bonding MO compare with the AO's
of the two atoms? What would this . I Illustrate imply about the location of the
bonding electron pair. with NaCl.
.m
Page 59 of 67
w
w
w
Molecular Structure
Questions
20. Sketch the use of AO's in bonding in the water molecule, assuming that
unhybridized s and three p orbitals of oxygen are used. What prediction does
this model make about the H-0-H bond angle?
21. Sketch the use of AO's in bonding in the water molecule, assuming that
hybrid sp AO's are the starting point for the oxygen atom. What does this
predict about the H-0-H bond angle? What is the observed bond angle, and
what does this tell us about the relative merits of the bond models of this
question and the preceding one?
22. What physical explanation can be given for the decrease of the H-0-H bond
angle in water from its ideal tetrahedral value? it explanation? How does this
compare with the VSEPR explanation?
om
23. When an sp hybrid AO on carbon interacts with a hydrogen 1s orbital, what
is the symmetry of the resulting MO's? Why are the antibonding MO's from such
combinations ordinarily ignored?
c
24. There is essentially free rotation about the carbon-carbon bond in ethane,
g.
although the "staggered" conformation, with hydro gens on one carbon rotated
ng
60 away from those on the other carbon, is 3 kcal mole more stable than the
"eclipsed" conformation, in which the hydrogens on opposite carbon atoms
overlap in a view down the carbon-carbon bond axis. Why should this energy
ye
difference, small as it is, exist?
25. Sketch the bonding in ethylene, assuming sp2 hybridization around the
.m
carbon atoms. In what sense would the bonding between carbons be a double
bond? What would this model predict for the H-C-H bond angle at each end of
w
the molecule?
w
Page 60 of 67
w
Molecular Structure
Questions
27. Use the sp3 model and then the sp2 model to predict what would happen to
the double bond when the two ends of the ethylene molecule are twisted9 How
does the real molecule behave, and which model is most compatible with
reality?
28. Sketch the o--bond skeleton of the ethylene molecule. Draw in the π MO of
the second bond. What is the electron probability density at each of the six
atoms in ethylene from the electrons in this π MO? Draw the nodal surface for
this orbital.
29. Sketch the σ-bond skeleton of the acetylene molecule. Draw in the π MO's
of the second and third bonds between carbon.
30. How does the carbon-carbon bond length change between ethane,
om
ethylene, and acetylene? How would you expect the bond energies to change?
31. Sketch the σ-bond skeleton of the benzene molecule. How many AO's and
c
how many bonding electrons are used in this σ- skeleton? What kind of
hybridization is used around the carbon atoms?
g.
ng
ye
Page 61 of 67
.m
w
w
w
Molecular Structure
Questions
32. How many bonding electrons, and how many and what kind of AO's, remain
unused in benzene after the o-hond skeleton is built? How are these electrons
and AO's used for further bonding in benzene? How does this resemble the
situation in ethylene and acety lene, and in what important way is it different?
33. How would the electrons and AO's not involved in the σ-bond skeleton be
used in the Kekule bond model for benzene? In a perspective view of the
hexagonal C ring, sketch the bonding π MO's.
34. Repeat the preceding question for one of the Dewar models of benzene.
35. In a similar perspective view of the benzene ring, sketch the actual MO,
showing the rings of electron probability above and below the C benzene-ring
plane.
om
36. For all of the π MO's in benzene, what is the electron probability density at
the carbon and hydrogen atoms? How does this compare with the density at the
C and H atoms for the π MO in ethylene? (See Question 28.)
c
g.
37. In what sense does bonding in the benzene molecule represent a step
ng
backward from two-atom bonds to full-molecule orbitals? What is this called?
What effect on the energy levels of a molecule accompanies such behavior?
Give examples of inorganic oxygencontaining compounds that show the same
ye
behavior.
.m
38. In what sense is it possible to think of the actual bonding in benzene as

being a "mixture" of Kekule and Dewar structures? What are these structures
called? Is any actual alternation back and forth between structures implied?
w
Page 62 of 67
w
w
Molecular Structure
Questions
39. In what ways can different resonance structures differ from one another,
and in what ways must they be alike? How is the number of different resonance
structures that can be drawn for a given molecule correlated approximately with
the energy of the molecule?
40. Sketch the σ-bond skeleton of the butadiene molecule. How many electrons
and AO's are used in this framework? What kind of hybridization is used around
the carbon atoms?
41. How many bonding electrons, and how many and what kind of AO's, remain
unused in butadiene after the σ-bond skeleton is built? How are these electrons
and AO's used for further bonding in butadiene? Over which atoms in the
molecule does delocalization extend?
om
42. Draw several resonance structures for butadiene. Show how each structure
assigns the four electrons not involved in σ- bonding among the four carbon
atoms.
c
g.
43. How do the energy levels in aromatic molecules change with an increase in
the extent of delocalization, and how is this reflected in the energy wavelengths
ng
of absorption or radiation?
44. How is the color that we see in a chemical compound related to the energy
ye
that it absorbs? If a molecule absorbs wavelengths in the blue region, why does
it appear orange to our eyes instead of blue?
.m
45. Why does absorption shift to longer wavelengths when the phenol molecule
dissociates to the phenolate ion? What prevents phenol from being a useful
w
acid-base indicator?
w
Page 63 of 67
w
Molecular Structure
Questions
46 . Why is alizarin a good acid-base indicator, whereas phenol is not?
47. Why is the ability to absorb visible light useful to living organisms? In what
way or ways is this ability especially useful to plants, and in what different way
is it useful to animals?
48. One objection to the supersonic transport (SST) is that waste oxides of
nitrogen emitted at high altitudes by the SST would combine with, and slowly
destroy, the high-altitude ozone layer around the planet. Recent calculations
have shown that a thermonuclear war would practically eliminate the ozone
layer. Why would the destruction of the ozone layer be dangerous to life (in
addition to the immediate hazards of the atomic war)?
49. What is the approximate wavelength range of the radiation that reaches the
om
surface of the Earth at the present time? What absorbs the longer and shorter
wavelengths and prevents them from reaching the surface?
c
g.
ng
ye
Page 64 of 67
.m
w
w
w
Molecular Structure
Problems
1. Where such combination is possible, sketch the initial arrangement of AO's
and final bonding and antibonding MO's for the combination of the following
AO's into MO's: (a) two s AO's into two σ- MO's (b) two p AO's into two π MO's
(6) two s AO's into two π MO's (d) two p AO's into two σ- MO's (e) an s and a p
AO into two σ- MO's (f) an s and a p AO into two π MO's For the impossible
combinations, explain why they are impossible.
2. Add the nodes, or surfaces of zero electron probability, to the sketches of

Problem 1. What relationship is there between the number of nodes in the
bonding and antibonding orbitals from the same two AO's? How does this arise
in the way the AO's are combined? How is this correlated with relative
energies?
3. If θ is the angular coordinate around the H-C C-H molecular axis in
om
acetylene, then the p wave functions (not the orbitals) have an angular
dependence given by ψ(θ) = sin θ, and the p wave functions have an angular
dependence ψ(θ) = cos θ. What then is the expression for the angular
c
dependence of the P
g.
and p atomic orbitals? Plot the two wave functions, and
the two atomic orbitals, on separate polar graphs and compare them.
ng
4. In view of the angular functions given in Problem 3, prove the statement in

the text that the combined π and π
ye
MO's in acetylene form a cylindrical

barrel of electron density, the same in all directions, θ, around the molecular
axis.
.m
5. The bond energies for typical carbon-carbon single and double bonds are 83
w
kcal mole and 147 kcal mole , respectively. Which of the following would
you expect as the triple bond energy: 106, 150, or 194 kcal mole ?
w
Page 65 of 67
w
Molecular Structure
Problems
6. The triple bond energies in acetylene, hydrogen cyanide, and nitrogen, are
194, 213, and 226 kcal mole , respectively. Diagram these three molecules,
showing the positions of all bonds and lone electron pairs. Why would one
expect the observed progression of bond energies? In singly bonded -N-N-N-N-
chains, it was stated previously that these were unstable in comparison with -C-
om
C-C-C- chains because of repulsions between nitrogen lone electron pairs. Why
is this apparently not a dominant factor in the comparison of HC CH, HCN,
and N ? Where are the lone pairs positioned in the N molecule?
c
7. The conventional numbering system for a three-ring carbon skeleton such as
g.
that of alizarin is
ng
ye
Hence the undissociated alizarin molecule shown previously in this chapter can
.m
be described as having carboryl (C=0) groups at Positions 9 and 10, and -OH
groups at Positions 1 and 2. The resonance model for the alizarin ion shown in
w
this chapter has -0 groups at Positions 1 and 2. Draw another resonance
structure with -0 groups at Positions 9 and 10 and carbonyl groups at 1 and 2.
w
What would this imply about shifts of electrons to and from the various oxygen
atoms?
w
Page 66 of 67
Molecular Structure
Problems
8. Continuing a search for resonance structures for the alizarin ion from
Problem 7, can you draw a structure in which carbonyl groups are present at
Positions 9 and 2, and -0 at 1 and 10? What about carbonyl groups at 9 and 1,
and -0 at 2 and 10? How many other resonance structures can you find that
differ in assignment of the negative charges to different pairs of oxygen?
om
9. How many different resonance structures can you draw for the alizarin ion in
which the negative charges are located on carbon atoms rather than on oxygen
atoms?
c
g.
10. As you try out various resonance models for the alizarin ion, you may come
across the empirical observation that only those structures are possible for
ng
which the carbon atoms bearing negative charges (either directly or through an
attached -0 ) are separated by an even number of other carbon atoms: 0, 2, 4, -
- -. Can you explain this in terms of single and double bonds between carbons
ye
in the three rings?
.m
w
w
w
Page 67 of 67
Page 1 of 1
c om
g.
ng
ye
.m
w
w
w
http://www.chem.ox.ac.uk/vrchemistry/pt/loader.swf 2006/12/11

Orbitals and Molecular Structure

Caricato da

Informazioni sul documento

Descrizione originale:

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Orbitals and Molecular Structure

Caricato da

Copyright:

Formati disponibili

Page 1 of 1

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

atom are as far as possible from the hydrogens on the

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

2. For a multiatorn molecule, what approximation are we using when we

6. Compare the theoretical predictions in Question 5 with the observed bond

terms of electron probability distributions.

9. Molecular Orbitals and -- Jump to --

model account for these unpaired electrons?

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

difference, small as it is, exist?

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

38. In what sense is it possible to think of the actual bonding in benzene as

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

9. Molecular Orbitals and -- Jump to --

2. Add the nodes, or surfaces of zero electron probability, to the sketches of

3. If θ is the angular coordinate around the H-C C-H molecular axis in

4. In view of the angular functions given in Problem 3, prove the statement in