26 Polyatomic molecules 

233

To prepare to generalize this expression we write αJ = HJJ The product on the left is
(with J = A or B), β = HAB, and label the overlap integrals with
⎛ H AA H AB ⎞ ⎛ c1, A c2 , A ⎞
their respective atoms, so S becomes SAB. We can introduce ⎜H =
⎝ BA H BB ⎟⎠ ⎜⎝ c1, B c2, B ⎟⎠
more symmetry into the equations by replacing the E in αJ – E
by ESJJ, with SJJ = 1. There is one further notational change. The ⎛ H AAc1, A + H ABc1, B H AAc2, A + H ABc2, B ⎞
⎜ H c +H c H BAc2, A + H BBc2, B ⎟⎠
coefficients cJ in the secular equations depend on the value of E, ⎝ BA 1, A BB 1, B
so we need to distinguish the two sets corresponding to the two
energies, which we denote E1 and E2. We therefore write them The product on the right is
as ci,J, with i = 1 (for energy E1) or 2 (for energy E2). With these
⎛ SAA SAB ⎞ ⎛ c1, A c2, A ⎞ ⎛ E1 0 ⎞ ⎛ SAA SAB ⎞ ⎛ c1, A E1 c2, A E2 ⎞
notational changes, the two equations become =
⎜S SBB ⎟⎠ ⎜⎝ c1, B c2, B ⎟⎠ ⎜⎝ 0 E2 ⎟⎠ ⎜⎝ SBA SBB ⎟⎠ ⎜⎝ c1, B E1 c2, B E2 ⎟⎠
⎝ BA
(H AA − Ei SAA )ci , A + (H AB − Ei SAB )ci , B =0 (26.5a) ⎛ E1SAAc1, A + E1SABc1, B E2SAAc2, A + E2SABc2, B ⎞
=⎜
⎝ E1SBAc1, A + E1SBBc1, B E2SBAc2, A + E2SBBc2, B ⎟⎠
(H BA − Ei SBA )ci , A + (H BB − Ei SBB )ci , B =0 (26.5b)
Comparison of matching terms (such as those in blue) re-
with i = 1 and 2, giving four equations in all. Each pair of equa- creates the four secular equations (two for each value of i).
tions can be written in matrix form as

⎛ H AA − Ei SAA H AB − Ei SAB ⎞ ⎛ ci , A ⎞
=0
⎜ H −E S
⎝ BA i BA H BB − Ei SBB ⎟⎠ ⎜⎝ ci , B ⎟⎠ In the Hückel approximation, HAA = HBB = α, HAB = HBA = β,
and we neglect overlap, setting S = 1, the unit matrix (with 1 on
because multiplying out the matrices gives eqn 26.5. If we the diagonal and 0 elsewhere). Then
introduce the following matrices and column vectors Hc = cE
⎛ H AA H AB ⎞ ⎛ SAA SAB ⎞ ⎛ ci , A ⎞ At this point, we multiply from the left by the inverse matrix
H =⎜ S=⎜ c = (26.6)
⎝ H BA H BB ⎟⎠ ⎝ SBA SBB ⎟⎠ i ⎜⎝ ci , B ⎟⎠ c−1, use c−1c = 1, and find

so that c −1 Hc = E (26.10)

⎛ H AA − Ei SAA H AB − Ei SAB ⎞ In other words, to find the eigenvalues Ei, we have to find a
H − Ei S = ⎜
⎝ H BA − Ei SBA H BB − Ei SBB ⎟⎠ transformation of H that makes it diagonal. This procedure is
called matrix diagonalization. The diagonal elements then cor-
then each pair of equations may be written more succinctly as respond to the eigenvalues Ei and the columns of the matrix c
that brings about this diagonalization are the coefficients of the
(H − Ei S)ci = 0 or Hci = Sci Ei (26.7) members of the basis set, the set of atomic orbitals used in the
calculation, and hence give us the composition of the molecu-
As shown in the following Justification, the two sets of equa- lar orbitals.
tions like these (with i = 1 and 2) can be combined into a single
matrix equation by introducing the matrices

⎛ c1, A c2 , A ⎞ ⎛ E1 0⎞ Example 26.1 Finding molecular orbitals by matrix

c = (c1 c2 ) = ⎜ E =⎜
c2, B ⎟⎠ E2 ⎟⎠
(26.8)
⎝ c1, B ⎝0 diagonalization
Set up and solve the matrix equations within the Hückel
for then all four equations in eqn 26.7 are summarized by the
approximation for the π orbitals of butadiene (1).
single expression
Hc = ScE (26.9)
1 Butadiene
Justification 26.1 The matrix formulation Method The matrices will be four-dimensional for this four-
Substitution of the matrices into eqn 26.9 gives atom system. Ignore overlap, and construct the matrix H by
using the Hückel approximation and the parameters α and
⎛ H AA H AB ⎞ ⎛ c1, A c2, A ⎞ ⎛ SAA SAB ⎞ ⎛ c1, A c2, A ⎞ ⎛ E1 0⎞ β. Find the matrix c that diagonalizes H: for this step, use
⎜H =
⎝ BA H BB ⎟⎠ ⎜⎝ c1, B c2, B ⎟⎠ ⎜⎝ SBA SBB ⎠⎟ ⎜⎝ c1, B c2, B ⎟⎠ ⎜⎝ 0 E2 ⎟⎠

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 234 6 Molecular structure

mathematical software. Full details are given in Mathematical Self-test 26.2 Repeat the exercise for the allyl radical,
background 5. ⋅CH2 eCHaCH2.
Answer: E = α + 1.41β, α, α – 1.41β; ψ1 = 0.500χA + 0.707χB + 0.500χ C,
Answer
ψ 2 = 0.707χA − 0.707χ C, ψ 3 = 0.500χA − 0.707χB + 0.500χ C
⎛ H11 H12 H13 H14 ⎞ ⎛α β 0 0 ⎞

⎜H H 22 H 23 H 24 ⎟ Huckel
⎜ β α β 0⎟
H =⎜ ⎟ ⎯approximation→⎜ ⎟
21
⎯⎯⎯⎯
⎜ H 31 H 32
⎜
H 33 H 34 ⎟
⎟
⎜ 0 β α β⎟
⎜ ⎟
26.2 Applications
⎝ H 41 H 42 H 43 H 44 ⎠ ⎝ 0 0 β α⎠
Although the Hückel method is very primitive, it can be
We write this matrix as used to account for some of the properties of conjugated
⎛0 1 0 0⎞ polyenes.
⎜1 0 1 0⎟
H = α 1+ β ⎜ ⎟
⎜0 1 0 1⎟ (a) Butadiene and π-electron binding energy
⎜ ⎟
⎝0 0 1 0⎠
As we saw in Example 26.1, the energies of the four LCAO-
MOs for butadiene are
because most mathematical software can deal only with
numerical matrices. The diagonalized form of the second E = α ± 1.62β , α ± 0.62β (26.11)
matrix is

⎛ +1.62 0 0 0 ⎞ These orbitals and their energies are drawn in Fig. 26.2. Note
⎜ 0 +0.62 0 0 ⎟ that the greater the number of internuclear nodes, the higher
⎜ ⎟ the energy of the orbital. There are four electrons to accommo-
⎜ 0 0 −0.62 0 ⎟
⎜ ⎟ date, so the ground-state configuration is 1π22π2. The frontier
⎝ 0 0 0 −1.62⎠
orbitals of butadiene are the 2π orbital (the HOMO, which is
so we can infer that the diagonalized hamiltonian matrix is largely bonding) and the 3π orbital (the LUMO, which is largely
antibonding). ‘Largely’ bonding means that an orbital has both
⎛ α + 1.62 β 0 0 0 ⎞ bonding and antibonding interactions between various neigh-
⎜ 0 α + 0.62 β 0 0 ⎟ bours, but the bonding effects dominate. ‘Largely antibonding’
E =⎜ ⎟ indicates that the antibonding effects dominate.
⎜ 0 0 α − 0.62 β 0 ⎟
⎜ ⎟ An important point emerges when we calculate the total
⎝ 0 0 0 α − 1 . 62 β ⎠
π-electron binding energy, Eπ, the sum of the energies of each
π electron, and compare it with what we find in ethene. In
The matrix that achieves the diagonalization is
ethene the total energy is
⎛ 0.372 0.602 0.602 −0.372⎞
⎜ 0.602 0.372 −0.372 0.602⎟ Eπ = 2(α + β ) = 2α + 2β
c =⎜ ⎟
⎜ 0.602 −0.372 −0.3372 −0.602⎟
⎜ ⎟
⎝ 0.372 −0.602 0.602 0.372⎠
4π
α – 1.62β + – + –
with each column giving the coefficients of the atomic orbitals
for the corresponding molecular orbital. We can conclude that
3π + +
the energies and molecular orbitals are α – 0.62β – –
C2p
E1 = α + 1.62β ψ 1 = 0.372χ A + 0.602χ B + 0.602χ C + 0.372χ D 2π
α + 0.62β + + – –
E2 = α + 0.62β ψ 2 = 0..602χ A + 0.372χ B − 0.372χ C − 0.602χ D
E3 = α − 0.62β ψ 3 = 0.602χ A − 0.372χ B − 0.372χ C + 0.602χ D 1π
α + 1.62β + + + +
E4 = α −1.62β ψ 4 = −0.372χ A + 0.602χ B − 0.602χ C + 0.372χ D

Figure 26.2 The Hückel molecular orbital energy levels of

where the C2p atomic orbitals are denoted by χA, …, χD. Note
butadiene and the top view of the corresponding π orbitals.
that the molecular orbitals are mutually orthogonal and, with
The four p electrons (one supplied by each C) occupy the two
overlap neglected, normalized.
lower π orbitals. Note that the orbitals are delocalized.

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 26 Polyatomic molecules  235

In butadiene it is Four electrons must be accommodated. Two occupy the lowest

orbital (of energy α + 2β), and two occupy the doubly degener-
Eπ = 2(α + 1.62β ) + 2(α + 0.62β ) = 4α + 4.48β ate orbitals (of energy α). The total energy is therefore 4α + 4β.
Two isolated π bonds would have an energy 4α + 4β; therefore,
Therefore, the energy of the butadiene molecule lies lower in this case, the delocalization energy is zero and there is no
by 0.48β (about 110 kJ mol−1) than the sum of two individual extra stability arising from delocalization.
π bonds. This extra stabilization of a conjugated system com-
Self-test 26.3 Repeat the calculation for benzene (use
pared with a set of localized π bonds is called the delocaliza-
software!).
tion energy of the molecule.
Answer: See next subsection
A closely related quantity is the π-bond formation energy,
Ebf, the energy released when a π bond is formed. Because the
contribution of α is the same in the molecule as in the atoms, (b) Benzene and aromatic stability
we can find the π-bond formation energy from the π-electron
binding energy by writing The most notable example of delocalization conferring extra
stability is benzene and the aromatic molecules based on its
Ebf = Eπ − N Cα Definition π-bond formation energy (26.12) structure. In elementary accounts, benzene and other aromatic
compounds are often described in a mixture of valence-bond
where NC is the number of carbon atoms in the molecule. The and molecular orbital terms, with typically valence-bond lan-
π-bond formation energy in butadiene, for instance, is 4.48β. guage used for its σ framework and molecular orbital language
used to describe its π electrons.
First, consider the valence-bond component. The six C atoms
Example 26.2 are regarded as sp2 hybridized, with a single unhybridized per-
Estimating the delocalization energy
pendicular 2p orbital. One H atom is bonded by (Csp2,H1s)
Use the Hückel approximation to find the energies of the π overlap to each C carbon, and the remaining hybrids overlap
orbitals of cyclobutadiene (2), and estimate the delocalization to give a regular hexagon of atoms (Fig. 26.3). The internal
energy. angle of a regular hexagon is 120°, so sp2 hybridization is ideally
suited for forming σ bonds. We see that the hexagonal shape of
benzene permits strain-free σ bonding.
2 Cyclobutadiene Now consider the molecular orbital component of the
description. The six C2p orbitals overlap to give six π orbitals
Method Set up the secular determinant using the same basis that spread all round the ring. Their energies are calculated
as for butadiene, but note that atoms A and D are also now within the Hückel approximation by diagonalizing the hamil-
neighbours. Then solve for the roots of the secular equation tonian matrix
and assess the total π-bond energy. For the delocalization
⎛α β 0 0 0 β ⎞
energy, subtract from the total π-bond energy the energy of
⎜β α β 0 0 0 ⎟
two π bonds. ⎜ ⎟
⎜0 β α β 0 0⎟
Answer The hamiltonian matrix is H =⎜ ⎟
⎜ 0 0 β α β 0⎟
⎛α β 0 β ⎞ ⎛0 1 0 1⎞ ⎜ 0 0 0 β α β⎟
⎜ β α β 0⎟ ⎜1 0 1 0⎟ Diagonalize ⎜ ⎟
H =⎜ ⎟ = α 1+ β ⎜ ⎟ ⎯⎯⎯⎯→ ⎝ β 0 0 0 β α⎠
⎜ 0 β α β⎟ ⎜0 1 0 1⎟
⎛0 1 0 0 0 1⎞ ⎛2 0 0 0 0 0 ⎞
⎜ ⎟ ⎜ ⎟
⎝ β 0 β α ⎠ ⎝1 0 1 0⎠ ⎜1 0 1 0 0 0⎟ ⎜0 1 0 0 0 0 ⎟
⎜ ⎟ ⎜ ⎟
⎛2 0 0 0⎞ ⎜0 1 0 1 0 0⎟ Diagonalize ⎜ 0 0 1 0 0 0⎟
⎜0 0 0 0⎟ = α 1+ β ⎜ ⎟ ⎯⎯⎯⎯→ ⎜ ⎟
⎜ ⎟ ⎜0 0 1 0 1 0⎟ ⎜0 0 0 −1 0 0 ⎟
⎜0 0 0 0⎟ ⎜0 0 0 1 0 1⎟ ⎜0 0 0 0 −1 0 ⎟
⎜ ⎟ ⎜ ⎟ ⎜ ⎟
⎝0 0 0 −2⎠ ⎝1 0 0 0 1 0⎠ ⎝0 0 0 0 0 −2 ⎠

Diagonalization gives the energies of the orbitals as

E = α + 2β , α , α , α − 2β
The MO energies, the eigenvalues of this matrix, are simply

E = α ± 2β , α ± β , α ± β (26.13)

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 236 6 Molecular structure

We now apply the building-up principle to the π system.

There are six electrons to accommodate (one from each C
atom), so the three lowest orbitals (a2u and the doubly degen-
H erate pair e1g) are fully occupied, giving the ground-state con-
C figuration a 22 u e14g . A significant point is that the only molecular
orbitals occupied are those with net bonding character.
The π-electron energy of benzene is

E = 2(α + 2β ) + 4(α + β ) = 6α + 8β

Figure 26.3 The σ framework of benzene is formed by If we ignored delocalization and thought of the molecule as
the overlap of Csp2 hybrids, which fit without strain into a having three isolated π bonds, it would be ascribed a π-electron
hexagonal arrangement. energy of only 3(2α + 2β) = 6α + 6β. The delocalization energy,
the difference between the π-electron energy and the energy
b2g
of the same molecule with localized π bonds, is therefore
+
– – 2β ≈ –460 kJ mol−1, which is considerably more than for butadi-
+ –
+ ene. The π-bond formation energy in benzene is 8β.
+ + – –
– e2u This discussion suggests that aromatic stability can be traced
– + – – to two main contributions. First, the shape of the regular hexa-
+
gon is ideal for the formation of strong σ bonds: the σ frame-
– work is relaxed and without strain. Second, the π orbitals are
– – + – such as to be able to accommodate all the electrons in bonding
e1g
+ +
+
orbitals, and the delocalization energy is large.
+ + –
+ +
+ + Example 26.3 Judging the aromatic character
+
a2u of a molecule
Decide whether the molecules C 4 H4 and the molecular ion
Figure 26.4 The Hückel orbitals of benzene and the C 4 H2+
4 are aromatic when planar.
corresponding energy levels. The symmetry labels are
Method Follow the procedure for benzene. Set up and solve the
explained in Topic 32. The bonding and antibonding character
secular equations within the Hückel approximation, assum-
of the delocalized orbitals reflects the numbers of nodes
ing a planar σ framework, and then decide whether the ion has
between the atoms. In the ground state, only the net bonding
nonzero delocalization energy. Use mathematical software to
orbitals are occupied.
diagonalize the hamiltonian (in Topic 32 it is shown how to use
symmetry to arrive at the eigenvalues more simply.)
as shown in Fig. 26.4. The orbitals there have been given sym- Answer It follows from Example 26.2 that the energy lev-
metry labels that are explained in Topic 32. Note that the low- els of the two species are E = α ± 2β, α, α. Because there are
est energy orbital is bonding between all neighbouring atoms, four π electrons to accommodate in C4H4, its total π-bonding
the highest energy orbital is antibonding between each pair energy is 2(α + 2β) + 2α = 4(α + β). The energy of two localized
of neighbours, and the intermediate orbitals are a mixture of π bonds is also 4(α + β). Therefore, the delocalization energy
bonding, nonbonding, and antibonding character between is zero and the molecule is not aromatic. There are only two
adjacent atoms. π electrons to accommodate in C 4 H2+ 4 , so the total π-bonding
The simple form of the eigenvalues in eqn 26.13 suggests that energy is 2(α + 2β) = 2α + 4β. The energy of a single localized
there is a more direct way of determining them than by using π bond is 2(α + β), so the delocalization energy is 2β and the
mathematical software. That is in fact the case, for symmetry molecular ion is aromatic.
arguments of the kind described in Topic 32 show that the 6 × 6 Self-test 26.4 What is the total π-bonding energy of C 3H3− ?
matrix can be factorized into two 1 × 1 matrices and two 2 × 2 Answer: [4α + 2β]
matrices, which are very easy to deal with.

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 26 Polyatomic molecules  237

Checklist of concepts
☐ 1. The Hückel method neglects overlap and interactions
between atoms that are not neighbours.
☐ 2. The Hückel method may be expressed in a compact
manner by introducing matrices.
☐ 3. The π-bond formation energy is the energy released
when a π bond is formed.
☐ 4. The π-electron binding energy is the sum of the ener-
gies of each π electron.
☐ 5. The delocalization energy is the difference between the
π-electron energy and the energy of the same molecule
with localized π bonds.
☐ 6. The highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO) form
the frontier orbitals of a molecule.
☐ 7. The stability of benzene arises from the geometry of the
ring and the high delocalization energy.

Checklist of equations
Property Equation Comment Equation number

χo are atomic orbitals

∑c χ
Linear combination of atomic orbitals (LCAO) 26.1
ψ= o o
o

Hückel equations Hc = ScE Hückel approximation: S = 1 26.9

Diagonalization c−1Hc = E Hückel approximation: S = 1 26.10

π-Bond formation energy Ebf = Eπ – NCα Hückel approximation: S = 1 26.12

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 TOPIC 27

Self-consistent fields
The field of computational chemistry, the use of computers
Contents to predict molecular structure and reactivity, has grown in the
27.1 The central challenge 238 past few decades due to the tremendous advances in computer
Brief illustration 27.1: The hamiltonian 239 hardware and to the development of efficient software pack-
27.2 The Hartree–Fock formalism 239 ages. The latter are now applied routinely to compute molecular
Brief illustration 27.2: A many-electron properties in a wide variety of chemical applications, includ-
wavefunction 240 ing pharmaceuticals and drug design, atmospheric and envi-
Brief illustration 27.3: The Hartree–Fock equations 241 ronmental chemistry, nanotechnology, and materials science.
27.3 The Roothaan equations 242 Many software packages have sophisticated graphical interfaces
Example 27.1: Setting up the Roothaan equations 242 that permit the visualization of results. The maturation of the
Example 27.2: Finding the energy levels 243 field of computational chemistry was recognized by the award-
Example 27.3: Establishing the integrals 244
ing of the 1998 Nobel Prize in Chemistry to J.A. Pople and
W. Kohn for their contributions to the development of compu-
Brief illustration 27.4: The integral notation 245
tational techniques for the elucidation of molecular structure
27.4 Basis sets 245
and reactivity.
Brief illustration 27.5: Minimal basis sets 245
Checklist of concepts 247
Checklist of equations 247

27.1 The central challenge

The goal of electronic structure calculations in computational
chemistry is the solution of the electronic Schrödinger equa-
➤ Why do you need to know this material?  = ΕΨ , where E is the electronic energy and Ψ is the
tion, HΨ
Modern computational procedures for predicting molecular many-electron wavefunction, a function of the coordinates of all
structure and reactivity are now widely available and used the electrons and the nuclei. To make progress, we invoke at the
throughout chemistry. Like any tool, it is important to know outset the Born–Oppenheimer approximation and the separa-
its foundations. tion of electronic and nuclear motion (Topic 22). The electronic
hamiltonian is
➤ What is the key idea?
Kinetic energy Their attraction Their mutual
Numerical procedures in computational chemistry typically of electrons to all the nuclei repulsion
proceed by solving equations until they converge, that is,       The
N N N N hamil-
(27.1)
2 e e n 2 e 2

∑ ∑∑ ∑
Z e 1 e
do not change on successive iterations. H = − ∇2 − I
+ tonian
2me i=1 i i=1 I =1 4 πε 0 rIi 2 i≠ j 4πε 0 rij
➤ What do you need to know already?
This Topic develops the approach introduced in Topic
26 and makes extensive use of matrix manipulations where rIi is the distance from electron i to nucleus I of charge
(Mathematical background 5). It is based on the variation Ze and rij is the electron–electron separation. The factor of 12 in
principle (Topic 25). the final sum ensures that each repulsion is counted only once.
The combination e2/4πε0 occurs throughout computational

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 27 Self-consistent fields  239

chemistry, and we shall denote it j0. Then the hamiltonian

becomes r12 Electron 2

Ne Ne Nn Ne Electron 1
2
∑ ∑∑ ∑
ZI 1 1
H = − ∇i2 − j0 + j rB2
2me i =1 i =1 I =1
rIi 2 0 i≠ j
rij rA1 rB1
rA2
We shall use the following labels:
Nucleus A Nucleus B
RAB

Species Label Number used Figure 27.1 The notation used for the description of
Electrons i and j = 1, 2, … Ne molecular hydrogen, introduced in Brief illustration 27.1 and
Nuclei I = A, B, … Nn used throughout the text.
Molecular orbitals, ψ m = a, b, … Nm*
which should be recognized as the hamiltonian for electron i
Atomic orbitals used to o = 1, 2, … Nb
construct the molecular
in an H2+ molecule-ion. Then
orbitals (the ‘basis’), χ
 = h + h + j0
H
* The number occupied in the ground state 1 2
r12

Another general point is that the theme we develop in the
sequence of Brief illustrations and Examples in this and related
Topics is aimed at showing explicitly how to use the equations
that are presented and thereby give them a sense of reality. To
do so, we shall take the simplest possible many-electron mole-
cule, dihydrogen (H2). Some of the techniques we introduce do
not need to be applied to this simple molecule, but they serve
to illustrate them in a simple manner and introduce problems
that successive sections show how to solve. One consequence
of choosing to develop a story in relation to H2, we have to
confess, is that not all the illustrations are actually as brief as
we would wish; but we decided that it was more important to
show the details of each little calculation than to adhere strictly
to our normal use of the term ‘brief ’. It is worthwhile to note
however that, although we restrict our examples to H2, calcula-
tions on larger molecules using computational software based
on methods described here and in related Topics may take only
a few seconds.
Brief illustration 27.1
The hamiltonian
The notation we use for the description of H2 is shown in Fig.
27.1. For this two-electron (Ne = 2), two-nucleus (Nn = 2) molecule
the hamiltonian is
 = −
(∇2 + ∇2 ) − j ⎛ 1 + 1 + 1 + 1 ⎞ + j0
2 that this orbital approximation is quite severe and loses many
H 0⎜
2me 1 2
⎝ rA1 rA 2 rB1 rB2 ⎟⎠ r12
To keep the notation simple, we introduce the one-electron
operator
2 2 ⎛ 1 1⎞
hi = − ∇ −j + spin α, electron 2 occupies the same orbital with spin β, and so
2me i 0 ⎜⎝ rAi rBi ⎟⎠
We see that the hamiltonian for H2 is essentially that of each
electron in an H2+ -like molecule-ion but with the addition of
the electron–electron repulsion term.
Self-test 27.1 What additional terms are needed for the
description of H3− ?
Answer: h3 + j0 /r13 + j0 /r23
It is hopeless to expect to find analytical solutions with a
hamiltonian of the complexity of that shown in eqn 27.1, even
for H2 with only a single electron–electron repulsion term, and
the whole thrust of computational chemistry is to formulate
and implement numerical procedures that give ever more reli-
able results.
27.2 The Hartree–Fock formalism
The electronic wavefunction of a many-electron molecule is a
function of the positions of all the electrons, Ψ(r1,r2,…). To
formulate one very widely used approximation, we build on
the material in Topic 24, where in the MO description of H2
it is supposed that each electron occupies an orbital and that
the overall wavefunction can be written ψ(r1)ψ(r2)…. Note
of the details of the dependence of the wavefunction on the
relative locations of the electrons. We do the same here, with
two small changes of notation. To simplify the appearance of
the expressions we write ψ(r1)ψ(r2)… as ψ(1)ψ(2)…. Next, we
suppose that electron 1 occupies a molecular orbital ψa with
on, and hence write the many-electron wavefunction Ψ as the
product Ψ =ψ aα (1)ψ aβ (2).... The combination of a molecular

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 240 6 Molecular structure

orbital and a spin function, such as ψ aα (1), is called a spinor-

We should recognize the spin factor as that corresponding
bital. For example, the spinorbital ψ aα should be interpreted as to a singlet state (eqn 19.2b, σ − = (1/21/2){αβ − βα}), so Ψ cor-
the product of the spatial wavefunction ψa and the spin state responds to two spin-paired electrons in ψ a. Note that inter-
α, so change of the electrons labelled 1 and 2 changes the sign of Ψ
spatial spin as required by the Pauli principle.

spinorbital

factor factor
ψ aα (1) = ψ a (1)α (1)
and likewise for the other spinorbitals. We shall consider only
closed-shell molecules but the techniques we describe can be
extended to open-shell molecules.
A simple product wavefunction does not satisfy the Pauli
principle and change sign under the interchange of any pair of
electrons (Topic 19). To ensure that the wavefunction does sat-
isfy the principle, we modify it to a sum of all possible permuta-
tions, using plus and minus signs appropriately:
Ψ =ψ aα (1)ψ aβ (2)ψ zβ (N e ) −ψ aα (2)ψ aβ (1)ψ zβ (N e ) +
There are Ne! terms in this sum, and the entire sum can be rep-
resented by a determinant called a Slater determinant, for its
expansion (see Mathematical background 5) generates the same
alternating sum of terms:
Self-test 27.2 Confirm that if any two rows of a Slater deter-
minant are interchanged, then the determinant changes sign.
Answer: Review properties of determinants,
Mathematical background 5
According to the variation principle (Topic 25) the best form
of Ψ is the one that corresponds to the lowest achievable energy
as the ψ are varied; that is, we need the wavefunctions ψ that
will minimize the expectation value ∫Ψ *ΗΨ dτ . Because the
electrons interact with one another, a variation in the form of
ψa, for instance, will affect what will be the best form of all the
other ψs, so finding the best form of the ψs is a far from trivial
problem. However, D.R. Hartree and V. Fock showed that the
optimum ψs each satisfy what is at first sight a very simple set
of equations:

ψ aα (1) ψ aβ (1)  ψ zβ (1) f1ψ a (1) = ε aψ a (1) Hartree–Fock equations (27.3)

1
Ψ= ψ a (2)
α
ψ a (2)
β
 ψ zβ (2) Slater
(N e !)1/2 determinant where f1 is called the Fock operator. This is the equation to
   
(27.2a) solve to find ψa; there are analogous equations for all the other
ψ a (N e ) ψ a (N e )  ψ z (N e )
α β β
orbitals. This Schrödinger-like equation has the form we should
expect (but its formal derivation is quite involved). Thus, f1 has
The factor 1/(Ne!)1/2 ensures that the wavefunction is normal- the following structure:
ized if the component molecular orbitals ψm are normalized.

Physical interpretation
To save the tedium of writing out large determinants, the f1 = core hamiltonian for electron 1 (h1 )
wavefunction is normally written by using only its principal + average Coulomb repulsion from
diagonal: electrons 2, 3,... (VCoulomb ) + average
correction due to spin correlation (Vexchange )
Ψ = (1/N e !)1/2 ψ aα (1)ψ aβ (2)ψ zβ (N e ) (27.2b) = h1 + VCoulomb + Vexchange

By the core hamiltonian we mean the one-electron hamilto-

Brief illustration 27.2 A many-electron wavefunction nian h1 defined in Brief illustration 27.1 and representing the
energy of electron 1 in the field of the nuclei. The Coulomb
The Slater determinant for the ground state of H2 (Ne = 2) is
repulsion from all the other electrons contributes a term that
1 ψ aα (1) ψ aβ (1) acts as follows (Fig. 27.2):
Ψ=
21/2 ψ aα (2) ψ aβ (2)
1
∫
Jm (1)ψ a (1) = j0 ψ a (1) ψ m* (2)ψ m (2)dτ 2
Coulomb
operator (27.4)
r12
where both electrons occupy the molecular wavefunction ψ a.
Expansion of the determinant gives This integral represents the repulsion experienced by electron
1 in orbital ψa from electron 2 in orbital ψm, where it is distrib-
Ψ=
1
21/2 a
{ }
ψ α (1)ψ aβ (2) −ψ aα (2)ψ aβ (1) uted with probability density ψm*ψm. There are two electrons in
each orbital, so we can expect a total contribution of the form
1
= 1/2 ψ a (1)ψ a (2) {α (1)β (2)−
− β (1)α (2)}
2 VCoulombψ a (1) = 2 ∑ J (1)ψ (1)
m , occ
m a (27.5)

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ψm
r12
ψa
Figure 27.2 A schematic interpretation of the Coulomb
repulsion term, eqn 27.4. An electron in orbital ψa experiences
repulsion from an electron in orbital ψm where it has
probability density |ψm|2.
where the sum is over all the occupied orbitals, including orbital
a. You should be alert to the fact that counting 2 for the orbital
with m = a is incorrect, because electron 1 interacts only with
the second electron in the orbital, not with itself. This error will
be corrected in a moment. The spin correlation term takes into
account the fact that electrons of the same spin tend to avoid
each other (Topic 20) which reduces the net Coulomb interac-
tion between them. This contribution has the following form:
1
K m (1)ψ a (1) = j0 ψ m (1) ψ m* (2)ψ a (2)dτ 2
∫
Exchange
operator
r12
For a given electron 1 there is only one electron of the same
spin in all the occupied orbitals of the closed-shell species we
are considering, so we can expect a total contribution of the
form
Vexchangeψ a (1) = − ∑ K
m , occ
m (1)ψ a (1)
The negative sign reminds us that spin correlation keeps elec-
trons apart, and so reduces their classical, Coulombic repul-
sion. By collecting terms, we arrive at a specific expression for
the effect of the Fock operator:
f1ψ a (1) = h1ψ a (1) + ∑ {2 J (1) − K (1)}ψ (1)
m , occ
m m a (27.8)
2 2
This expression applies to all the molecular orbitals, but the
sum extends over only the Nm occupied orbitals. Note that
K a (1)ψ a (1) = Ja (1)ψ a (1), so the term in the sum with m = a
loses one of its 2Ja , which is the correction that avoids the elec-
tron repelling itself, which we referred to above.
Equation 27.8 reveals a second principal approximation of
the Hartree–Fock formalism (the first being its dependence
on the orbital approximation). Instead of electron 1 (or any
other electron) responding to the instantaneous positions of
the other electrons in the molecule through terms of the form
1/r1j, it responds to an averaged location of the other electrons
Atkins09819.indb 241
27 Self-consistent fields  241
through integrals of the kind that appear in eqn 27.8. We say
that the Hartree–Fock method ignores electron correlation,
the instantaneous tendency of electrons to avoid one another to
minimize repulsions. This failure to take into account electron
correlation is a principal reason for inaccuracies in the calcula-
tions and leads to calculated energies that are higher than the
‘true’ (that is, experimental) values.
Although eqn 27.8 is the equation we have to solve to find
ψa, it implies that it is necessary to know all the other occu-
pied wavefunctions in order to set up the operators J and K
and hence to find ψa. To make progress with this difficulty, we
can guess the initial form of all the one-electron wavefunc-
tions, use them in the definition of the Coulomb and exchange
operators, and solve the Hartree–Fock equations. That process
is then continued using the newly found wavefunctions until
each cycle of calculation leaves the energies εm and wavefunc-
tions ψm unchanged to within a chosen criterion. This is the
origin of the term self-consistent field (SCF) for this type of
procedure in general and of Hartree–Fock self-consistent field
(HF-SCF) for the approach based on the orbital approximation.
(A brief description of the HF-SCF method as applied to many-
electron atoms is provided in Topic 19.)
(27.6)
Brief illustration 27.3 The Hartree–Fock equations
We continue with the H2 example. According to eqn 27.8, the
Hartree–Fock equation for ψ a is f1ψ a (1) = ε aψ a (1) with
f1ψ a (1) = h 1ψ a (1) + 2 Ja (1)ψ a (1) − K a (1)ψ a (1)
(27.7) where
1
∫
Ja (1)ψ a (1) = K a (1)ψ a (1) = j0 ψ a (1) ψ a* (2)ψ a (2)dτ 2
r12
Note that there is only one occupied orbital in this case so the
summation in eqn 27.8 is a single term. The equation to solve
is therefore
−
2me 1 a
⎛ 1
∇ ψ (1) − j0 ⎜
1⎞
+ ⎟ ψ a (1)
⎝ A1 B1 ⎠
r r
1 *
∫
+ j0 ψ a (1) ψ (2)ψ a (2)dτ 2 = ε aψ a (1)
r12 a
This equation for ψ a must be solved self-consistently (and
numerically) because the integral that governs the form of ψ a
requires us to know ψ a already. In the following examples we
shall illustrate some of the procedures that have been adopted.
Self-test 27.3 Identify the additional terms that would arise in
a closed-shell four-electron homonuclear diatomic molecule
in which two electrons also occupy a molecular orbital b.
Answer: +2 Jb (1)ψ a (1) − K b (1)ψ a (1)
9/11/2013 11:35:23 AM
 242 6 Molecular structure

Once the Hartree–Fock equations have been solved for the S is the Nb × Nb matrix of overlap integrals:
spatial wavefunctions ψ, the ground-state wavefunction Ψ
(eqn 27.2) can be constructed and the SCF energy computed ∫
So ′o = χ o ′ (1)χ o (1)dτ 1 Overlap matrix elements (27.11b)
from the expectation value ∫Ψ * HΨdτ . The final, complicated,
expression is a sum over all the electrons in the molecule, of c is an Nb × Nb matrix of all the coefficients we have to find:
integrals involving the wavefunctions ψ.1
⎛ c1a c1b  c1N b
⎞
⎜c c2 b  c2 N ⎟
c =⎜ ⎟
2a b
Matrix of coefficients (27.11c)
⎜     ⎟
27.3 The Roothaan equations ⎜
 cN N
⎟
⎝ cN a b
cN b b b b ⎠
The difficulty with the HF-SCF procedure lies in the numeri-
cal solution of the Hartree–Fock equations, an onerous task and ε is an Nb × Nb diagonal matrix with the values ε1 , ε 2 ,…, ε N b

even for powerful computers. As a result, a modification of the along the diagonal; of these eigenvalues, the first Nm refer to the
technique was needed before the procedure could be of use to occupied orbitals.
chemists. Topic 23 explains how molecular orbitals are con-
structed as linear combinations of atomic orbitals. This simple
approach was adopted in 1951 by C.C.J. Roothaan and G.G. Justification 27.1 The Roothaan equations
Hall independently, who found a way to convert the Hartree–
Fock equations for the molecular orbitals into equations for To construct the Roothaan equations we substitute the linear
the coefficients that appear in the LCAO used to simulate the combination of eqn 27.9 with m = a into both sides of eqn 27.3,
which gives
molecular orbital. Thus, they wrote
Nb Nb

Nb f1ψ a (1) = f1 ∑c oa χ o (1) = ε a ∑c oa χ o (1)

ψm = ∑o=1
com χ o A general LCAO (27.9) o=1 o=1

Now multiply from the left by χ o ′ (1) and integrate over the
coordinates of electron 1:
where com are unknown coefficients and the χo are the (known)
atomic orbitals (which we take to be real). This LCAO approxi- Nb  Fo′o
 Nb S
o ′o

mation is in addition to the approximations underlying the
Hartree–Fock equations because the basis is finite and so can-
∑c ∫
o=1
oa χ (1)f χ (1)dτ  = ε
o′ 1 o 1 a ∑ c ∫χ
o=1
oa o ′ (1)χ o (1)dτ 1

not reproduce the molecular orbital exactly. The size of the

basis set (Nb) is not necessarily the same as the number of That is,
atomic nuclei in the molecule (Nn), because we might use sev- ( Fc )o′a
   ( Sc )o′a
  
eral atomic orbitals on each nucleus (such as the four 2s and 2p Nb Nb

orbitals of a carbon atom). From Nb basis functions, we obtain ∑ Fo ′ocoa = ε a ∑S o ′ocoa

Nb linearly independent molecular orbitals ψm, some (Nm) of o=1 o=1

which will be occupied. The remaining, unoccupied linear

combinations are called virtual orbitals.
We show in the following Justification that the use of a linear
combination like eqn 27.9 leads to a set of simultaneous equa-
tions for the coefficients called the Roothaan equations. These
equations are best summarized in matrix form by writing
Fc = Scε Roothaan equations (27.10)
where F is the Nb × Nb matrix with elements
Fo ′o = χ o ′ (1) f1 χ o (1)dτ 1
∫ Fock matrix elements (27.11a)
1 For details, see our Molecular quantum mechanics, Oxford University
Press (2011).
This expression has the form of the matrix equation in eqn
27.10.
Example 27.1 Setting up the Roothaan equations
Set up the Roothaan equations for H2.
Method Adopt a basis set of real, normalized functions χA and
χB, centred on nuclei A and B, respectively. We can think of
these functions as H1s orbitals on each nucleus, but they could
be more general than that, and in a later Example we shall
make a computationally more friendly choice. Then establish
the c, S, and F matrices.

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 27 Self-consistent fields  243

Answer The two possible linear combinations corresponding of coefficients is given by eqn 27.11c and can be written in the
to eqn 27.9 are ψ m = cAm χ A + cBm χ B , with m = a (occupied) and form
b (virtual), so the matrix c is
c = (c (a ) , c (b) ,…c ( N b ) )
⎛ cAa cAb ⎞
c =⎜ where c(m) is the column vector composed of the coefficients
⎝ c Ba cBb ⎟⎠
com for the molecular orbital ψ m of energy εm:
and the overlap matrix S of the individually normalized ⎛ c1m ⎞
atomic orbitals is ⎜c ⎟
c (m) = ⎜ ⎟
2m
⎛ 1 S⎞ ⎜  ⎟
S=⎜ ⎟
⎝ S 1⎠ ∫
S = χ A χ B dτ ⎜ ⎟
⎝ cN b m ⎠

The Fock matrix is In terms of these column vectors, the equation Mc = cε con-
sists of the set of equations of the form Mc (m) = ε mc (m), or
⎛ FAA FAB ⎞ (M − εm1)c(m) = 0. As explained in Mathematical background 5,
F =⎜
⎝ FBA FBB ⎟⎠ ∫
FXY = χ X f1 χ Y dτ
this set of equations has nontrivial solutions (c(m) ≠ 0) only if

We explore the explicit form of the elements of F in a later M − ε m 1 = 0, or S −1F − ε m 1 = 0

Example; for now, just regard them as variable quantities. The The roots of this secular equation are the energies ε m, m = 1,
Roothaan equations are therefore 2, … N b (the elements of the diagonal matrix ε). Multiplication
cAb ⎞ ⎛ ε a of both sides by the determinant |S| and using the property of
⎛ FAA FAB ⎞ ⎛ cAa cAb ⎞ ⎛ 1 S⎞ ⎛ cAa 0⎞
⎜F = determinants that |AB| = |A| × |B| results in
⎝ BA FBB ⎟⎠ ⎜⎝ cBa cBb ⎟⎠ ⎜⎝ S 1⎟⎠ ⎜⎝ cBa cBb ⎟⎠ ⎜⎝ 0 ε b ⎟⎠
| F −ε mS | =0
After multiplying out these matrices and matching the ele-
The set of equations Mc(m) = εmc(m) holds for all m = 1, 2, …, N b
ments corresponding to the occupied orbital a, we obtain
and solution of the secular equation results in all (N b) energies
FAAcAa + FABcBa = ε acAa + ε a ScBa ε, so we can drop the subscript m and thereby obtain eqn 27.12.
FBAcAa + FBBcBa = ε acBa + ε a ScAa

Thus, to find the coefficients for the molecular orbital ψ a we

need to solve this pair of simultaneous equations.
Self-test 27.4 Write the additional two equations for the vir-
tual orbital b constructed from the same basis.
Answer: FAAcAb + FABcBb = εbcAb + εbScBb, FBAcAb + FBBcBb = εbcBb + εbScAb
The Roothaan equations, eqn 27.10, are simply a collection
of Nb simultaneous equations for the Nb coefficients com. We
can use the properties of matrices and determinants as shown
in the following Justification to show that the energies are the
solutions of the secular equation
| F − ε S |= 0
Justification 27.2 The secular determinant
To determine the form of the secular determinant arising
from the Roothaan equations, we begin by multiplying both
sides of eqn 27.10 by S −1, the matrix inverse of S, and, in the
resulting expression S −1Fc = cε, denote the matrix product
S −1F by M. The equation then becomes Mc = cε. The matrix c
In principle, we can find the orbital energies ε by looking
for the roots of this equation and then using those energies to
find the coefficients that make up the matrix c by solving the
Roothaan equations. There is a catch, though: the elements of F
depend on the coefficients (through the presence of J and K in
the expression for f1 ). Therefore, we have to proceed iteratively:
we guess an initial set of values for c, solve the secular equation
for the orbital energies, use them to solve the Roothaan equations
for c, and compare the resulting values with the ones we started
with. In general they will be different, so we use those new values
in another cycle of calculation, and continue until convergence
has been achieved (Fig. 27.3). For small, closed-shell molecules,
the convergence is often achieved within a few cycles.
(27.12)
Example 27.2 Finding the energy levels
Solve the secular equations for the H2 molecule established in
Example 27.1.
Method Set up the secular determinant for the orbitals using
the notation in Example 27.1, expand it, and find the roots of
the resulting quadratic equation.

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 244 6 Molecular structure

Answer The secular determinant for the H2 molecule is

∫
Foo ′ = χ o h1 χ o ′ dτ
FAA − ε FAB − ε S
∑ ∫ χ (1)χ
1
=0 + 2 j0 o o′ (1) ψ (2)ψ m (2)dτ 1dτ 2
FBA − ε S FBB − ε m , occ
r12 m (27.13)

∑ ∫ χ (1)ψ
1
The determinant expands to give the following equation: − j0 o m (1) ψ (2) χ o ′ (2)dτ 1dτ 2
m , occ
r12 m
(FAA − ε )(FBB − ε ) − (FAB − Sε )(FBA − Sε ) = 0

On collecting terms, we arrive at where the sums are over the occupied molecular orbitals. The
dependence of F on the coefficients can now be seen to arise
(1 − S 2 )ε 2 − (FAA + FBB − SFAB − SFBA )ε + (FAA FBB − FAB FBA ) = 0
from the presence of the ψm in the two integrals, for these
This is a quadratic equation for the orbital energies ε a and εb, molecular orbitals depend on the coefficients in their LCAOs.
and may be solved by using the quadratic formula. Thus, if we
summarize the equation as aε2 + bε + c = 0, then Example 27.3 Establishing the integrals
a = 1− S2
Expand the matrix element FAA developed in Example 27.2 in
−b ± (b2 − 4ac)1/2
ε= b = −(FAA + FBB − SFAB − SFBA ) terms of molecular integrals.
2a
c = FAA FBB − FAB FBA Method Implement eqn 27.13.

With these energies established, and the lower value accepted Answer Only one molecular orbital is occupied, so eqn 27.13
for εa, we can construct the coefficients by substituting into becomes
1
cAa = −
FAB − Sε a
c
FAA − ε a Ba ∫
FAA = χ Ah1 χ A dτ + 2 j0 χ A (1) χ A (1) ∫ ψ (2)ψ a (2)dτ 1dτ 2
r12 a
1
i n conju nc t ion w it h t he nor ma l i z at ion cond it ion ∫
− j0 χ A (1)ψ
ψ a (1) ψ (2) χ A (2)dτ 1dτ 2
r12 a
c 2Aa + c Ba
2
+ 2cAacBa S = 1. (For this homonuclear diatomic mol-
ecule, there is, of course, a much simpler method of arriving at With ψ a = cAaχA + cBaχB, the second integral on the right is
cAa = cBa for the lower of the two energies.) 1
Self-test 27.5 Use the orbital energy εb to write the expressions ∫χ (1)χ (1) r ψ (2)ψ (2)dτ dτ
A A
12
a a 1 2

1
relating cAb and cBb.
FBB − εb = ∫ χ (1)χ (1) {c χ (2) + c χ (2)}
A A Aa A Ba B
Answer: cAb = − c , c 2 + c 2 + 2cAbcBb S = 1 r 12
FBA − Sεb Bb Ab Bb
× {cAa χ A (2) + cBa χ B (2)} dτ 1dτ 2
1

The principal outstanding problem is the form of the ele-

∫
= cAacAa χ A (1)χ A (1) χ (2)χ A (2)dτ 1dτ 2 +
r12 A

ments of the Fock matrix F and its dependence on the LCAO with four such terms. At this point we can see explicitly that
coefficients. The explicit form of Foo′ is the matrix elements of F depend on the coefficients that we are
trying to find.
Self-test 27.6 Write the integral that is a factor of the term
Choose set of Formulate set of trial cAa cBa.
basis functions, χo
∫χ
coefficients com and 1
Answer: A (1)χ A (1) χ (2)χ B (2)dτ 1dτ 2
therefore wavefunctions ψm r12 A
Fock matrix,
Overlap matrix, F, eqn 27.11a
S, eqn 27.11b Done The integrals that appear in expressions like those developed
No Yes in this Example are becoming seriously cumbersome to write.
From now on we shall use the notation
Energies, εm Convergence?
coefficients, com ;
1
eqn 27.12 (AB|CD) = j0 χ A (1) χ B (1)∫ χ (2) χ D (2)dτ 1dτ 2
r12 C
(27.14)

Figure 27.3 The iteration procedure for a Hartree–Fock self- Integrals like this are fixed throughout the calculation (for a
consistent field calculation. particular nuclear geometry) because they depend only on the

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choice of basis, so they can be tabulated once and for all and
then used whenever required. How they are estimated or calcu-
lated is explained in Topics 28–30. For the time being, we can
treat them as constants.
Brief illustration 27.4 The integral notation
In the notation of eqn 27.14, the integral written explicitly in
Example 27.3 becomes
1
∫
j0 χ A (1) χ A (1) ψ a (2)ψ a (2)dτ 1dτ 2
r12
= cA2 a (AA|AA) + 2cAacBa (AA|BA) + cB2 a (AA|BB)
(We have used (AA|BA) = (AA|AB).) There is a similar term for
the third integral in the expression for FAA developed there,
and overall
FAA = EA + cA2 a (AA|AA) + 2cAacBa (AA|BA)
+ cB2 a {2(AA|BB) − (AB|BA)}
where
∫
EA = χ Ah 1 χ A dτ
is the energy of an electron in orbital χA based on nucleus A,
taking into account its interaction with both nuclei. Similar
expressions may be derived for the other three matrix ele-
ments of F. The crucial point, though, is that we now see how F
depends on the coefficients that we are trying to find.
Self-test 27.7 Construct the element FAB using the same basis.
∫
Answer: FAB = χ A h1 χ B dτ + cA
2 (BA|AA)
a
+ cAa cBa {3(BA|AB) − (AA|BB)}
+ cB2 a (BA|BB)
27.4 Basis sets
One of the problems with molecular structure calculations
now becomes apparent. The basis functions appearing in eqn
27.14 may in general be centred on different atomic nuclei so
(AB|CD) is in general a so-called ‘four-centre, two-electron
integral’. If there are several dozen basis functions used to build
the one-electron wavefunctions, there will be tens of thousands
of integrals of this form to evaluate (the number of integrals
increases as N4b).The efficient calculation of such integrals poses
the greatest challenge in an HF-SCF calculation but can be alle-
viated by a clever choice of basis functions.
The simplest approach is to use a minimal basis set, in which
one basis function is used to represent each of the orbitals in an
Atkins09819.indb 245
27 Self-consistent fields  245
elementary valence theory treatment of the molecule. Minimal
basis set calculations, however, frequently yield results that are
far from agreement with experiment and the development of
basis sets that go beyond the minimal basis is an active area of
research within computational chemistry.
Brief illustration 27.5 Minimal basis sets
The following choices for constituent atoms correspond to
minimal basis sets:
H, He Li to Ne Na to Ar
1 (1s) 5 (1s, 2s, 2p) 9 (1s, 2s, 2p, 3s, 3p)
Thus, a minimal basis set for CH4 consists of nine functions:
four basis functions to represent the four H1s orbitals, and one
basis function each for the 1s, 2s, 2px, 2py, and 2pz orbitals of
carbon.
Self-test 27.8 How many orbitals would constitute a minimal
basis set for PF5 (discounting d orbitals)?
Answer: 34
One of the earliest choices for basis-set functions was that of
Slater-type orbitals (STO) centred on each of the atomic nuclei
in the molecule and of the form
χ = Nr a e − br Ylm (θ , φ )
l
Slater-type orbitals (27.15)
N is a normalization constant, a and b are (non-negative)
parameters, Ylm is a spherical harmonic (Table 14.1), and (r,
l
θ, φ) are the spherical polar coordinates describing the loca-
tion of the electron relative to the atomic nucleus. Several such
basis functions are typically centred on each atom, with each
basis function characterized by a unique set of values of a, b, l,
and ml. The values of a and b generally vary with the element
and there are several rules for assigning reasonable values. For
molecules containing hydrogen, there is an STO centred on
each proton with a = 0 and b = 1/a0, which simulates the correct
behaviour of the 1s orbital at the nucleus. However, using the
STO basis set in HF-SCF calculations on molecules with three
or more atoms requires the evaluation of so many two-electron
integrals (AB|CD) that the procedure becomes computation-
ally impractical.
The introduction of Gaussian-type orbitals (GTO) by S.F.
Boys largely overcame the problem. Cartesian Gaussian func-
tions centred on atomic nuclei have the form
χ = Nx i y j z k e −α r
2
Gaussian-type orbitals (27.16)
where (x, y, z) are the Cartesian coordinates of the electron at
a distance r from the nucleus, (i, j, k) are a set of non-negative
9/11/2013 11:36:09 AM
 246 6 Molecular structure

– +
G1G2 (magnified)
+ – + G1
+ –

G(x)
G2
(a) (b) (c)

Figure 27.4 Contour plots for Gaussian-type orbitals: (a) s-type

Gaussian, e −r ; (b) p-type Gaussian, xe − r ; (c) d-type Gaussian,
2 2

−r2
xye . x

Figure 27.5 The product of two Gaussian functions on

integers, and α is a positive constant. An s-type Gaussian has
i = j = k = 0; a p-type Gaussian has i + j + k = 1; a d-type Gaussian
has i + j + k = 2, and so on. Figure 27.4 shows contour plots for
various Gaussian-type orbitals. The advantage of GTOs is
that, as we show in the following Justification, the product of
two Gaussian functions on different centres is equivalent to a
single Gaussian function located at a point between the two
centres (Fig. 27.5). Therefore, two-electron integrals on three
and four different atomic centres can be reduced to integrals
over two different centres, which are much easier to evaluate
different centres is itself a Gaussian function located at a
point between the two contributing Gaussians. The scale
of the product has been increased relative to that of its two
components.
numerically. This advantage generally outweighs the disad-
vantage of using Gaussian functions, namely that, on account
of the e −α r term, GTOs do not simulate the correct behaviour
2
of the 1s orbital at the nucleus, and as a result more Gaussian
functions are needed than for a calculation using STOs.

Justification 27.3 Gaussian-type orbitals

There are no four-centre integrals in H2 , but we can illustrate we can confirm that
the principle by considering one of the two-centre integrals that 2 2 2
appear in the Fock matrix, and, to be definite, we consider r1 − RA + r1 − RB = 12 R2 + 2 r1 − RC

1 where RC = 12 (RA + RB ) is the midpoint of the molecule and

(AB|AB) = j0 ∫ χ A (1)χ B (1) χ A (2)χ B (2)dτ 1dτ 2
r12 R = |R A − R B| is the bond length. Hence

 χ 
C (1)

We choose an s-type Gaussian basis and write 2
χ A (1) χ B (1) = e −α R /2 N 2e α r1 −RC
−2
2

2 2
χ A (1) = Ne −α r1 −RA χ B (1) = Ne −α r1 −RB The product χA(2)χB(2) is the same, except for the index 2 in
place of 1 on r. Therefore, the two-centre, two-electron integral
where r1 is the location of electron 1 and R I is that of nucleus I. (AB|AB) reduces to
The product of these two Gaussians is
1
(AB|AB) = j0e −α R ∫χ χ (2)dτ 1dτ 2
2
C (1)
2
2 −α r1 −RA −α r1 −RB
2
r12 C
χ A (1)χ B (1) = N e
This is a single-centre, two-electron integral, with both expo-
By using the relation
nential functions spherically symmetrical Gaussians centred on
2 2 2 the midpoint of the bond, and much faster to evaluate than the
r − R = (r − R)⋅(r − R) = r + R − 2r ⋅ R
original two-centre integral.

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 27 Self-consistent fields  247

Checklist of concepts
☐ 1. A spinorbital is the product of a molecular orbital and a
spin function.
☐ 2. A Slater determinant expresses the fact that the inter-
change of any pair of electrons changes the sign of the
wavefunction.
☐ 3. The Hartree–Fock (HF) method uses a single Slater
determinant, built from molecular orbitals that satisfy
the HF equations, to represent the ground-state elec-
tronic wavefunction.
☐ 4. In the self-consistent field (SCF) method, equations are
solved iteratively until each cycle of calculation leaves
the energies and wavefunctions unchanged to within a
chosen criterion.
☐ 5. The Hartree–Fock equations involve the Fock operator,
which consists of the core hamiltonian and terms rep-
resenting the average Coulomb repulsion (J) and aver-
age correction due to spin correlation (K).
☐ 6. The Hartree–Fock method neglects electron correla-
tion, the tendency of electrons to avoid one another to
minimize repulsion.
☐ 7. The Roothaan equations are a set of simultaneous
equations, written in matrix form, that result from
using a basis set of functions to expand the molecular
orbitals.
☐ 8. In a minimal basis set, one basis set function represents
each of the valence orbitals of the molecule.
☐ 9. Slater-type orbitals (STO) and Gaussian-type orbitals
(GTO) centred on each of the atomic nuclei are com-
monly used as basis set functions.
☐ 10. The product of two Gaussian-type orbitals on different
centres is a single Gaussian function located between
the centres.

Checklist of equations
Property Equation Comment Equation number

Many-electron wavefunction Ψ = (1/N e !)1/2 ψ aα (1)ψ aβ (2)ψ zβ (N e ) Closed-shell species 27.2

Hartee–Fock equations f1ψ m (1) = ε mψ m (1) m labels an occupied molecular 27.3

orbital

Coulomb operator
∫
Jm (1)ψ a (1) = j0 ψ a (1)(1/ r12 )ψ m
* (2)ψ (2)dτ
m 2 j0 = e2/4πε0 27.4

Exchange operator
∫
K m (1)ψ a (1) = j0 ψ m (1)(1/r12 )ψ m
* (2)ψ (2)dτ
a 2 27.6

Effect of Fock operator f1ψ a (1) = h1ψ a (1) +

∑{2J (1)− K
m
m m (1)}ψ a (1) Sum over occupied orbitals 27.8

Roothaan equations Fc = Scε 27.10

Fock matrix elements

∫
Fo ′o = χ o ′ (1) f1 χ o (1)dτ 1 χo are atomic basis functions 27.11

Four-centre integral
∫
(AB|CD) = j0 χ A (1) χ B (1)(1/r12 ) χ C (2) χ D (2)dτ 1dτ 2 Notation 27.14

Slater-type orbital χ = Nr a e −brYlml (θ , φ ) STO 27.15

χ = Nx i y j z k e −α r
2
Gaussian-type orbital GTO 27.16

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 TOPIC 28
Semi-empirical methods
Contents
28.1 The Hückel approximation revisited
Brief illustration 28.1: The Hückel method
28.2 Differential overlap
Brief illustration 28.2: Neglect of differential
overlap
Checklist of concepts
Checklist of equations
➤ Why do you need to know this material?
Modern computational procedures include semi-empirical
methods, and it is important to know their approximations.
These methods are useful because they can be applied
with computational efficiency to complex systems.
➤ What is the key idea?
Semi-empirical procedures typically identify integrals
that may either be neglected or replaced by empirical
parameters.
➤ What do you need to know already?
You should review the Hartree–Fock and Roothaan
procedures introduced in Topic 27 and should be familiar
with the Hückel approximation (Topic 26).
In semi-empirical methods, many of the integrals that occur
in an electronic structure calculation are estimated by appeal-
ing to spectroscopic data or physical properties such as ioniza-
tion energies, or by using a series of rules to set certain integrals
equal to zero. These methods are applied routinely to molecules
containing large numbers of atoms because of their computa-
tional speed but there is often a sacrifice in the accuracy of the
results.
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Atkins09819.indb 248
28.1The Hückel approximation
revisited
248
248
249 Semi-empirical methods were first developed for conjugated
π systems, the most famous version being Hückel molecular
249 orbital theory (HMO theory, Topic 26).
250 The initial assumption of HMO theory is the separate treat-
250 ment of π and σ electrons, which is justified by the different
energies and symmetries of the orbitals. As explained in Topic
26, the π-orbital energies and wavefunctions are obtained by
solution of eqn 26.9 of that Topic (Hc = ScE); the latter equation
is composed of sets of matrix equations of the form of eqn 26.7,
(H – EiS)ci = 0, where Ei is an element of the diagonal matrix E.
This equation implies (see Mathematical background 5) that we
need to find solutions of the secular determinant |H – EiS| = 0
with, in HMO theory, the overlap integrals set to 0 or 1, the
diagonal hamiltonian matrix elements set to a parameter α,
and off-diagonal elements set either to 0 or to the parameter β.
If instead we start from eqn 27.12 of Topic 27 (|F – εS| = 0), then
we can generate HMO theory by making similar choices for the
integrals. The HMO approach is useful for qualitative, rather
than quantitative, discussions of conjugated π systems because
it treats repulsions between electrons very poorly.
Brief illustration 28.1 The Hückel method
Here we return to Example 27.2 of Topic 27 and set S = 0. The
diagonal Fock matrix elements are set equal to α (that is, we
set FAA = FBB = α), and the off-diagonal elements are set equal
to β (that is, we set FAB = FBA = β). Note that the dependence of
these integrals on the coefficients is swept aside, so we do not
have to work towards self-consistency. The quadratic equation
for the energies
(1 − S 2 )ε 2 − (FAA + FBB − SFAB − SFBA )ε + (FAA FBB − FAB FBA ) = 0
9/11/2013 11:36:35 AM
 28 Semi-empirical methods  249

becomes simply The ‘differential overlap’ term χA(1)χB(1) is set equal to zero,
so in the CNDO approximation the integral is set equal to
ε 2 − 2αε + α 2 − β 2 = 0
zero. The same is true of the integral (AA|BA). It follows that
we write
and the roots are ε = α ± β, exactly as we found in Topic 25.
Self-test 28.1 What would the energies be if overlap were not FAA = EA + cA2 a (AA|AA) + 2cB2 a (AA|BB)
neglected?
Answer: (α + β)/(1 + S) and (α – β)/(1 – S) and identify the surviving two two-electron integrals as
empirical parameters.
Self-test 28.2 Apply the CNDO approximation to FAB for the
same system.
Differential overlap
28.2
∫
Answer: FAB = χ A h1 χ B dτ − cAa cBa (AA|BB)

In the second most primitive and severe approach, called com-

plete neglect of differential overlap (CNDO), all two-electron
integrals of the form (AB|CD) introduced in Topic 27, More recent semi-empirical methods make less draconian
decisions about which integrals are to be ignored, but they
1
∫
(AB|CD) = j0 χ A (1) χ B (1) χ (2) χ D (2)dτ 1dτ 2
r12 C
(28.1) are all descendants of the early CNDO technique. Whereas
CNDO sets integrals of the form (AB|AB) to zero for all dif-
are set to zero unless χA and χB are the same, and likewise for χC ferent χ A and χ B, intermediate neglect of differential over-
and χD. That is, only integrals of the form lap (INDO) does not neglect the (AB|AB) for which different
basis functions χA and χ B are centred on the same nucleus.
1 Because these integrals are important for explaining energy
∫
(AA|CC) = j0 χ A (1)2 χ (2)2 dτ 1dτ 2
r12 C
(28.2)
differences between terms corresponding to the same elec-
tronic configuration, INDO is much preferred over CNDO
survive and they are often taken to be parameters with values for spectroscopic investigations. A still less severe approxima-
adjusted until the calculated energies are in agreement with tion is neglect of diatomic differential overlap (NDDO) in
experiment. The origin of the term ‘differential overlap’ is that which (AB|CD) is neglected only when χ A and χ B are centred
what we normally take to be a measure of ‘overlap’ is the inte- on different nuclei or when χ C and χ D are centred on different
gral ∫χAχBdτ. The differential of an integral of a function is the nuclei.
function itself, so in this sense the ‘differential’ overlap is the There are other semi-empirical methods, with names such
product χAχB. The implication is that we then simply compare as modified intermediate neglect of differential overlap
orbitals: if they are the same, the integral is retained; if different, (MINDO), modified neglect of differential overlap (MNDO),
it is discarded. Austin model 1 (AM1), PM3, and pairwise distance directed
Gaussian (PDDG). In each case, the values of integrals are
Brief illustration 28.2 Neglect of differential overlap either set to zero or set to parameters with values that have been
determined by attempting to optimize agreement with experi-
The expression for FAA derived in Brief illustration 27.4 of ment, such as measured values of enthalpies of formation,
Topic 27 is dipole moments, and ionization energies. MINDO is useful for
FAA = EA + cA2 a (AA|AA) + 2cAacBa (AA|BA) the study of hydrocarbons; it tends to give more accurate com-
puted results than MNDO but it gives poor results for systems
+ cB2 a {2(AA|BB) − (AB|BA)}
with hydrogen bonds. AM1, PM3, and PDDG are improved
versions of MNDO.
The final (blue) integral has the form
1
∫
(AB|BA) = j0 χ A (1) χ B (1) χ (2) χ A (2)dτ 1dτ 2
r12 B

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 250 6 Molecular structure

Checklist of concepts
☐ 1. In semi-empirical methods, the two-electron integrals
are set to zero or to empirical parameters with values
that optimize agreement with a variety of experimental
quantities.
☐ 2. The Hückel method is a simple semi-empirical method
for conjugated π systems.
☐ 3. In the complete neglect of differential overlap (CNDO)
approximation, two-electron integrals are set to zero
unless the two basis set functions for electron 1 are the
same and the two basis functions for electron 2 are the
same.

Checklist of equations
Property Equation Comment Equation number

Molecular integrals
∫
(AB|CD) = j0 χ A (1) χ B (1)(1/ r12 ) χ C (2) χ D (2)dτ 1dτ 2 Parameterized in a variety of ways 28.1

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 TOPIC 29
Ab initio methods
Contents
29.1 Configuration interaction
Brief illustration 29.1: Configuration interaction
Example 29.1: Finding the energy lowering
due to CI
29.2 Many-body perturbation theory
Example 29.2: Setting up Møller–Plesset
perturbation theory
Checklist of concepts
Checklist of equations
➤ Why do you need to know this material?
Modern computational procedures focus on the formu-
lation of reliable ab initio methods. To use commercially
available software sensibly and to understand the
underlying problems it is important to know how they are
being overcome.
➤ What is the key idea?
Ab initio procedures typically seek to compute molecular
structures and properties from first principles without
introducing empirical constants.
➤ What do you need to know already?
You should review the Hartree–Fock and Roothaan
procedures introduced in Topic 27 and be familiar with
Slater determinants (Topic 27) and time-independent
perturbation theory (Topic 15).
In ab initio methods, the two-electron integrals (AB|CD) intro-
duced in Topic 27 are evaluated numerically. However, even for
small molecules, Hartree–Fock calculations with large basis
sets and efficient and accurate calculation of two-electron inte-
grals can give very poor results because they are rooted in the
orbital approximation and the average effect of the other elec-
trons on the electron of interest. Thus, the true wavefunction
Atkins09819.indb 251
for H2 is a function of the form Ψ(r1,r2), with a complicated
behaviour as r1 and r2 vary and perhaps approach one another.
251 This complexity is lost when the wavefunction is written as
252 ψ(r1)ψ(r2) and each electron is treated as moving in the average
field of the other electrons. That is, the approximations of the
252 Hartree–Fock method imply that no attempt is made to take
253 into account electron correlation, the tendency of electrons to
stay apart in order to minimize their mutual repulsion.
254 Most modern work in electronic structure, such as the approach-
254 es discussed here as well as more sophisticated approaches that
255 are beyond the scope of this text, tries to take electron correla-
tion into account. Here we give an introduction to just two of the
procedures. Topic 30 (density functional theory) presents another
way to take electron correlation into account.
29.1 Configuration interaction
A basis set of Nb orbitals can be used to generate Nb molecular
orbitals. However, if there are Ne electrons to accommodate, in
the ground state only Nm = 12 Ne of these Nb orbitals are occu-
pied, leaving Nb − 12 Ne so-called virtual orbitals unoccupied.
For example, in the H2 model calculation used in Topics 27 and
28 the two atomic orbitals give rise to a bonding and an anti-
bonding molecular orbital, but only the former is occupied; the
latter is present but ‘virtual’.
The ground state of an Ne-electron closed-shell species is
Ψ0 = (1/N e!)1/2 ψ aα (1)ψ aβ (2)ψ bα (3)ψ bβ (4)ψ uβ (N e )
where ψu is the highest occupied molecular orbital (the
HOMO). We can envisage transferring an electron from an
occupied orbital to a virtual orbital ψv, and forming the cor-
responding singly excited determinant, such as
Ψ1 = (1/N e!)1/2 ψ aα (1)ψ aβ (2)ψ bα (3)ψ vβ (4)ψ uβ (N e )
Here a β electron, ‘electron 4’, has been promoted from ψb into
ψv, but there are many other possible choices. We can also
9/11/2013 11:36:45 AM
 252 6 Molecular structure

envisage doubly excited determinants, and so on. Each of the
Slater determinants constructed in this way is called a configu-
ration state function (CSF).
In 1959, P.-O. Löwdin proved that the exact wavefunc-
tion (within the Born–Oppenheimer approximation) can be
expressed as a linear combination of CSFs found from the exact
solution of the Hartree–Fock equations:
Ψ = C0Ψ0( ) + C1Ψ1( ) + C2Ψ2( ) + . . . Configuration (29.1)
interaction
The inclusion of CSFs to improve the wavefunction in this way
is called configuration interaction (CI). Configuration inter-
action can, at least in principle, yield the exact ground-state
wavefunction and energy and thus accounts for the electron
correlation neglected in Hartree–Fock methods. However, the
wavefunction and energy are exact only if an infinite number of
CSFs (composed using an infinite number of basis-set orbitals)
are used in the expansion in eqn 29.1; in practice, we have to be
resigned to using a finite number of CSFs (composed from a
finite basis set). One simplification, however, is that there might
be symmetry arguments that eliminate the need to include cer-
tain contributions.
Brief illustration 29.1 Configuration interaction
We can begin to appreciate why CI improves the wavefunc-
tion of a molecule by considering H2 . The ground state (after
expanding the Slater determinant) is Ψ 0 = ψ a(1)ψ a(2)σ − (1,2)
where σ− (1,2) is the singlet spin state wavefunction. We also
know that if we use a minimal basis set and ignore overlap, we
can write ψ a =1/21/2 { χ A + χ B }. Therefore
Ψ0 = 12 { χ A (1) + χ B (1)}{ χ A (2) + χ B (2)}σ − (1, 2)
= 12 { χ A (1)χ A (2) + χ A (1)χ B (2) + χ B (1)χ A (2)
Brief illustration 29.1 shows that even a limited amount of
CI can introduce some electron correlation; full CI—using
orbitals built from a finite basis and allowing for all possible
excitations—will take electron correlation into account more
fully. The optimum procedure, using orbitals that form an
infinite basis and allowing all excitations, is computationally
impractical.
The optimum expansion coefficients in eqn 29.1 are found
by using the variation principle. As in Justification 27.1 for the
Hartree–Fock method, application of the variation principle
for CI results in a set of simultaneous equations for the expan-
sion coefficients.
Example 29.1 Finding the energy lowering due to CI
Set up the equations that must be solved in order to find the
optimum values of the expansion coefficients for a CI treat-
ment of H2.
Method Use the Ψ = C 0Ψ 0 + C 2Ψ 2 superposition from Brief
illustration 29.1. We do not need to consider the singly excited
determinant because it is of opposite symmetry to the ground
state (which is g, Topic 23) of dihydrogen. Set up the secular
equation |H – ES| = 0 and express the integrals in terms of the
(AB|CD) notation introduced in Topic 27 (eqn 27.14):
1
∫
(AB|CD) = j0 χ A (1) χ B (1) χ (2) χ D (2)dτ
r12 C
The hamiltonian is H  = h 1 + h 2 + j / r . For integrals of the
0 12
form ∫dτ over the wavefunctions Ψ, which involve spin as
well as space variables, interpret the integration as over both
sets of variables, with the spin integration over the normalized
spin state σ_(1,2) interpreted as
∫ σ (1, 2) dτ = 1
−
2

+ χ B (1)χ B (2)}σ − (1, 2)

Answer The 2 × 2 H and S matrices are
We can see a deficiency in this wavefunction: there are equal
⎛ H 00 H 02 ⎞
∫
probabilities of finding both electrons on A or on B (the blue  Ψ dτ
H =⎜ H MN = ΨM H
terms) as there are for finding one electron on A and the other ⎝ H 20 H 22 ⎟⎠ N

on B (the remaining two terms). That is, electron correlation ⎛ S00 S02 ⎞
has not been taken into account and we can expect the calcu-
lated energy to be too high.
S=⎜
⎝ S20 S22 ⎟⎠ MN ∫
S = ΨMΨ N dτ

Self-test 29.1 Show t hat t he superposition of a dou- Note that the overlap integral is between the two-electron
bly excited determinant Ψ 2 based on the virtual orbital wavefunctions, not the overlap of individual atomic orbitals.
ψ b =1/21/2 { χ A − χ B } reduces the probability that both elec- The secular equation to solve to find E is
trons will be found on the same atom.
H 00 − ES00 H 02 − ES02
Answer: Ψ = C0Ψ0 + C2Ψ2 = 12 {A χ A (1)χ A (2) + B χ A (1)χ B (2) =0
H 20 − ES20 H 22 − ES22
+ B χ B (1)χ A (2) + A χ B (1)χ B (2)}
×σ − (1, 2), A = C0 + C2 < B = C0 − C2
(Note that S02 = S20 and H02 = H20 due to hermiticity.)

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 29 Ab initio methods  253

The molecular orbitals ψ a and ψb are orthogonal, so

29.2 Many-body perturbation theory
ψ0 ψ0
     
∫ ∫
Ψ0Ψ0dτ = ψ a (1)ψ a (2)σ − (1, 2)ψ a (1)ψ a (2)σ − (1, 2) dτ The application of perturbation theory to a molecular system
of interacting electrons and nuclei is called many-body pertur-

1  
1  
1 

bation theory. According to the presentation of perturbation
∫ ∫
= ψ a (1)2 dτ 1 ψ a (2)2 dτ 2 σ − (1, 2)2 dσ = 1 ∫ theory in Topic 15 (see eqn 15.1, H = H + H (1) ), the hamil-
(0)

ψ2 ψ0
        tonian is expressed as a sum of a simple, ‘model’ hamiltonian,
∫ ∫
Ψ2Ψ0dτ = ψ b (1)ψ b (2)σ − (1, 2) ψ a (1)ψ a (2)σ − (1, 2) dτ ∫ H , and a perturbation, H . Because we wish to find the cor-
(0) (1)


0  
0  
1 
 relation energy, a natural choice for the model hamiltonian is
the sum of Fock operators of the HF-SCF method,
∫ ∫
= ψ b (1)ψ a (1)dτ 1 ψ b (2)ψ a (2)dτ 2 σ − (1, 2)2 dσ = 0 ∫ f = h i +
and likewise for S02 and S22. That is, S = 1. The secular determi-
i ∑ {2 J
m
m (i) − K m (i)} (29.2)

nant is now easily rearranged into a quadratic equation for E

and for the perturbation it is the difference between this sum
with solutions
and the true many-electron hamiltonian. That is,
{
E = 12 ( H 00 + H 22 ) ± 12 (H 00 + H 22 )2 − 4(H 00 H 22 − H 02 }
1/2
2
) Ne

= 12 (H 00 + H 22 ) ± 12 {(H 00 − H 22 )2 + 4 H 02
2
}
1/2 H = H (0) + H (1) with H (0) = ∑ f
i =1
i
(29.3a)

As usual, the problem boils down to an evaluation of various with

integrals that appear in the matrix elements. Ne

To evaluate the H00 hamiltonian matrix elements, we note ∑ h i

   i =1

that N N N Ne
2 e e n

∑ ∑∑ ∑r
ZI 1 1
H = − ∇2 − j + j (29.3b)
⎛ j ⎞ 2me i=1 i 0 i=1 I =1 rIi 2 0
H 00 = Ψ0 ⎜ h 1 + h 2 + 0 ⎟Ψ0dτ
∫ i≠ j ij

⎝ r12 ⎠
Because the core hamiltonian (the sum of the h i in the Fock
The first term in this integral (noting that the spin integration, operator in eqn 29.2) cancels the one-electron terms in the full
as previously, gives 1) is: hamiltonian, the perturbation is the difference between the
instantaneous interaction between the electrons (the blue term
∫Ψ h Ψ dτ = ∫ψ (1)ψ (2)h ψ (1)ψ (2)dτ dτ
0 1 0 a a 1 a a 1 2 in eqn 29.3) and the average interaction (as represented by the
    1 
Ea operators J and K in the Fock operator). Thus, for electron 1,

∫ 
= ψ (1) h ψ (1)dτ ψ (2)ψ (2)dτ = E
a 1 a 1 ∫ a a 2 a
 (1) (1) =
∑ r − ∑ {2 J
j0
H m (1) − K m (1)} (29.4)
The integral with h 2 in place of h 1 has the same value. For the
i 1i m

electron–electron repulsion term, where the first sum (the true interaction) is over all the elec-
1 1 trons other than electron 1 itself and the second sum (the aver-
∫
j0 Ψ0 ∫
Ψ dτ = j0 ψ a (1)ψ a (2) ψ a (1)ψ a (2)dτ 1dτ 2
r12 0 r12 age interaction) is over all the occupied orbitals. This choice
= 14 {(AA|AA) + (AA|AB) +(BB|BB)} was first made by C. Møller and M.S. Plesset in 1934 and the
method is called Møller–Plesset perturbation theory (MPPT).
Expressions of a similar kind can be developed for the other Applications of MPPT to molecular systems were not under-
three elements of H, so the optimum energy can be found by taken until the 1970s and the rise of sufficient computing
substituting these matrix elements of H into the solutions E. power.
The coefficients in the CI expression for Ψ can then be found As usual in perturbation theory, the true wavefunction is
in the normal way by using the lower value of E and solving written as a sum of the eigenfunction of the model hamiltonian
the secular equations. and higher-order correction terms. The correlation energy, the
Self-test 29.2 Establish the expression for H02. difference between the true energy and the HF energy, is given
by energy corrections that are second-order and higher. If we
Answer: H 02 = 14 {(AA|AA) − (AA|AB) + (BB|BB)} suppose that the true wavefunction of the system is given by a
sum of CSFs like that in eqn 29.1, then

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 254 6 Molecular structure

∫Ψ  (1) Ψ 0 dτ
H (As before, integration of spin states has given 1.) All the
∑
M Møller–Plesset
E0(2) = perturbation (29.5) integrals over terms based on J and K are zero because these
E (0)
−E (0)
M ≠0 0 M theory are one-electron operators and so either ψ a(1) or ψ a(2) is left
unchanged and its orthogonality to ψ b ensures that the inte-
According to Brillouin’s theorem, only doubly excited Slater gral vanishes. We now expand each molecular orbital in terms
determinants have nonzero H  (1) matrix elements and hence
of the basis functions χA and χB, and obtain
only they make a contribution to E0(2).1 The identification of the
second-order energy correction with the correlation energy is 1
∫Ψ H {(AA|AA) − (BA|AA) + + (BB|BB)}
(1)
the basis of the MPPT method denoted MP2. The extension of 2 Ψ 0 dτ =
2
MPPT to include third- and fourth-order energy corrections
are denoted MP3 and MP4, respectively. On usi ng sy m met r ies l i ke (A A|A B) = (A A|BA) a nd
(AA|AB) = (BB|BA), this expression simplifies to
Example 29.2 Setting up Møller–Plesset perturbation
1
∫Ψ H {(AA|AA) − (AA|BB)}
(1)
theory 2 Ψ 0 dτ =
2
Use the MP2 procedure to set up an expression for the correla-
tion energy in the model of H2 that we have been developing. It follows that the second-order estimate of the correlation
energy is
Method According to Brillouin’s theorem, and for our simple
model of H2 built from two basis orbitals, we write Ψ = C0Ψ0 + C2Ψ2
with, as before, Ψ0 = ψa(1)ψa(2)σ −(1,2) and Ψ2 = ψb(1)ψb(2)σ −(1,2). E0(2) =
1
4 {(AA|AA) − (AA|BB)}2 = {(AA|AA) − (AA|BB)}2
E0(0) − E M
(0) 8(ε a − ε b )
Formulate the integrals that appear in eqn 29.5.
Answer The only matrix element we need for the sum in eqn The term (AA|AA)–(AA|BB) is the difference in repulsion
29.5 is energy between both electrons being confined to one atom
and each being on a different atom.
1
∫Ψ H ∫
(1)
2 Ψ0dτ = j0 ψ b (1)ψ b (2) ψ (1)ψ a (2)dτ 1dτ 2
r12 a Self-test 29.3 Demonstrate the validity of the last remark.

Checklist of concepts
☐ 1. Electron correlation is the tendency of electrons to stay
apart in order to minimize their mutual repulsion.
☐ 2. Virtual orbitals are molecular orbitals that are unoc-
cupied in the HF ground-state electronic wavefunction.
☐ 3. A singly excited determinant is formed by transferring
an electron from an occupied orbital to a virtual orbital,
a doubly excited determinant by transferring two elec-
trons, and so on.
☐ 4. Each of the Slater determinants (including the HF
wavefunction) is a configuration state function (CSF).
☐ 5. Configuration interaction (CI) expresses the exact
electronic wavefunction as a linear combination of con-
figuration state functions.
☐ 6. Configuration interaction and Møller–Plesset pertur-
bation theory are two popular ab initio methods that
accommodate electron correlation.
☐ 7. Full CI uses molecular orbitals built from a finite basis
set and allows for all possible excited determinants.
☐ 8. The correlation energy is the difference between the
true energy and the energy calculated by the Hartree–
Fock procedure.
☐ 9. Many-body perturbation theory is the application of
perturbation theory to a molecular system of interact-
ing electrons and nuclei.
☐ 10. Møller–Plesset perturbation theory (MPPT) uses the
sum of the Fock operators from the HF method as the
simple, model hamiltonian.
☐ 11. According to Brillouin’s theorem, only doubly excited
determinants contribute to the second-order energy
correction.

1 For details, see our Molecular quantum mechanics, Oxford University Press (2011).

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 29 Ab initio methods  255

Checklist of equations

Property Equation Comment Equation number

Configuration interaction Ψ = C0Ψ0( ) + C1Ψ1( ) + C2Ψ2( ) + . . . 29.1

Møller–Plesset perturbation theory H (1) (1) =

∑ j /r − ∑ {2J
i
0 1i
m
m (1) − K m (1) }. 29.4

2
Correlation energy in MPPT E0(2) =
∑ ∫Ψ
M ≠0
MH
 (1)Ψ dτ
0 (E0(0) − EM(0) ) . MP2 29.5

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 TOPIC 30

Density functional theory

30.1 The Kohn–Sham equations
Contents
30.1 The Kohn–Sham equations 256 The central focus of DFT is the electron probability density,
30.2 The exchange–correlation energy 257 ρ. The ‘functional’ part of the name comes from the fact that
(a) The exchange–correlation potential 257 the energy of the molecule is a function of the electron density
Example 30.1: Deriving an exchange–correlation and the electron density is itself a function of the positions of
potential 257 the electrons, ρ(r). In mathematics a function of a function is
(b) Solution of the equations 258 called a functional, and in this specific case we write the energy
Example 30.2: Applying the DFT method 258 as the functional E[ρ]. We have encountered a functional else-
Checklist of concepts 259 where but did not use this terminology: the expectation value
Checklist of equations 259 of the hamiltonian is the energy expressed as a functional of the
wavefunction, for a single value of the energy, E[ψ], is associ-
ated with each function ψ. An important point to note is that
because E[ψ] is an integral of ψ Hψ over all space, it has contri-
butions from the whole range of values of ψ.
➤ Why do you need to know this material? Simply from the structure of the hamiltonian in Topic 27
Density functional theory is currently a highly popular (eqn 27.1),
method for the calculation of electronic structure, and
Kinetic energy Their attraction
it is important to know the general features of the of electrons to all thenuclei
procedure.    
N N N
2 e e n
Z I e2
➤ What is the key idea?
H = −
2me i=1 ∑
∇i2 − ∑∑
i =1 I =1
4 πε 0 rIi
The
The energy of a molecule can be calculated from the hamiltonian (30.1)
Their mutual
electron density. repulsion

N e
e2
➤ What do you need to know already? + 12 ∑
i≠ j
4 πε 0 rij
You need to be aware of the structure of the hamiltonian
for a polyatomic molecule (Topic 27).
we can suspect that the energy of a molecule can be expressed
as contributions from the kinetic energy, the electron–nuclear
interaction, and the electron–electron interaction. The first two
A technique that has gained considerable ground in recent contributions depend on the electron density distribution. The
years to become one of the most widely used procedures for electron–electron interaction is likely to depend on the same
the calculation of molecular structure is density functional quantity, but we have to be prepared for there to be a modi-
theory (DFT). Its advantages include less demanding com- fication of the classical electron–electron interaction due to
putational effort, less computer time, and—in some cases, electron exchange (the contribution which in Hartree–Fock
particularly for d-metal complexes—better agreement with theory is expressed by K). That the exchange contribution can
experimental values than is obtained from Hartree–Fock be expressed in terms of the electron density is not at all obvi-
based methods. ous, but in 1964 P. Hohenberg and W. Kohn were able to prove

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 30 Density functional theory  257

that the exact ground-state energy of an Ne-electron molecule
is uniquely determined by the electron probability density.
They showed that it is possible to write
E[ ρ] = Eclassical[ ρ] + EXC[ ρ] Energy functional
gets its value from the entire range of values of ρ(r), not just
from a single point. Thus, when r undergoes a small change,
dr, the density changes by δρ to ρ(r + dr) at each point and
EXC[ρ] undergoes a change that is the sum (integral) of all such
(30.2) changes:

where Eclassical[ρ] is the sum of the contributions of kinetic energy, δEXC[ ρ ]

electron–nucleus interactions, and the classical electron–elec-
δEXC[ ρ ] = ∫ δρ ∫
δρ dr = VXC (r )δ ρ dr (30.6)

tron potential energy, and EXC[ρ] is the exchange–correlation

energy. This term takes into account all the non-classical elec-
tron–electron effects due to spin and applies small corrections to
the kinetic energy part of Eclassical that arise from electron–elec-
tron interactions. The Hohenberg–Kohn theorem guarantees
the existence of EXC[ρ] but—like so many existence theorems in
mathematics—gives no clue about how it should be calculated.
The first step in the implementation of this approach is to
calculate the electron density. The relevant equations were
deduced by W. Kohn and L.J. Sham in 1965, who showed that
ρ can be expressed as a contribution from each electron present
in the molecule, and written
Ne
Note that VXC is an ordinary function of r, not a functional: it
is the local contribution to the integral that defines the global
dependence of EXC[ρ] on δρ throughout the range of integra-
tion. This procedure is clarified and illustrated in Example 30.1.
(a) The exchange–correlation potential
The greatest challenge in density functional theory is to find an
accurate expression for the exchange–correlation energy. One
widely used but approximate form for EXC[ρ] is based on the
model of a uniform electron gas, a hypothetical electrically
neutral system in which electrons move in a space of continu-

∑|ψ (r )|
ous and uniform distribution of positive charge. For a uniform
ρ(r ) = i
2

i =1
Electron density
The function ψi is called a Kohn–Sham orbital and is a solution
of the Kohn–Sham equation, which closely resembles the form
of the Schrödinger equation (on which it is based). For a two-
electron system,
(30.3) electron gas, the exchange–correlation energy can be written as
the sum of an exchange contribution and a correlation contri-
bution. The latter is a complicated functional that is beyond the
scope of this Topic; we ignore it here. The following example
shows how to infer the exchange–correlation potential for the
exchange contribution.

ρ(2)
h1ψ i (1) + j0∫ dτ 2ψ i (1) + VXC (1)ψ i (1) Kohn– Example 30.1 Deriving an exchange–correlation
r12 Sham (30.4) potential
= ε iψ i (1) equation
The exchange–correlation energy for a uniform electron gas
The first term is the usual core term, the second term is the is1
classical interaction between electron 1 and electron 2, and ⎛ 3⎞
1/ 2

the third term takes exchange effects into account and is ∫

EXC[ ρ ] = A ρ 4/3dr A = − 89 ⎜ ⎟
⎝ π⎠
j0
called the exchange–correlation potential. The εi are the
Kohn–Sham orbital energies. with, as usual, j 0 = e 2 /4πε 0 . Deduce the corresponding
exchange–correlation potential.
Method Identify how the functional EXC[ρ] changes when the
The exchange–correlation
30.2 density changes from ρ(r) to ρ(r) + δρ(r) at each point (Fig.
energy 30.1), and then use a Taylor series (Mathematical background
1) to expand the integrand. Compare the result with eqn 30.6
to identify V XC(r).
The exchange–correlation potential plays a central role in DFT
and can be calculated once we know the exchange–correlation Answer When the density changes from ρ(r) to ρ(r) + δρ(r)
energy EXC[ρ] by forming the following ‘functional derivative’: the functional changes from EXC[ρ] to EXC[ρ + δρ]:

δE [ ρ ]
VXC (r ) = XC Exchange–correlation potential (30.5)
∫
EXC [ρ + δ ρ] = A (ρ + δ ρ)4/3 dr
δρ

A functional derivative is defined like an ordinary deriva- 1 For the origin of this term, see our Molecular quantum mechanics,

tive, but we have to remember that EXC[ρ] is a quantity that Oxford University Press (2011).

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 258 6 Molecular structure

(b) Solution of the equations

The Kohn–Sham equations must be solved iteratively and
Contribution to energy

E[ρ + δρ]
self-consistently (Fig. 30.2). First, we guess the electron
density; it is common to use a superposition of atomic elec-
E[ρ] tron probability densities. Second, the exchange–correlation
potential is calculated by assuming an approximate form
of the dependence of the exchange–correlation energy on
ρ(r) ρ(r) + δρ(r) the electron density and evaluating the functional deriva-
tive. Next, the Kohn–Sham equations are solved to obtain
an initial set of Kohn–Sham orbitals. This set of orbitals is
Location used to obtain a better approximation to the electron prob-
ability density (from eqn 30.3) and the process is repeated
Figure 30.1 The change in the exchange–correlation energy
until the density remains constant to within some specified
functional from EXC[ρ] to EXC[ρ + δρ] (the area under each
tolerance. The electronic energy is then computed by using
curve) as the density changes from ρ to ρ + δρ at each point r.
eqn 30.2.
Expand the integrand in a Taylor series in the vicinity of ρ: As is the case for the Hartree–Fock one-electron wavefunc-
4
tions, the Kohn–Sham orbitals can be expanded using a set
ρ 1/3
3  of Nb basis functions; solving eqn 30.4 then amounts to find-
⎛ d(ρ + δ ρ)4 /3 ⎞ ing the coefficients in the expansion. Various basis functions,
( ρ + δ ρ )4 / 3 = ρ 4 / 3 +⎜ ⎟⎠ δρ + 
⎝ dρ including Slater-type orbitals (STO) and Gaussian-type orbitals
δρ = 0
(GTO), can be used (Topic 27). Whereas Hartree–Fock meth-
=ρ 4 /3
+ ρ δρ + 
4
3
1/ 3
ods have computational times that scale as N b4 , DFT methods
scale as N b3 . Therefore, DFT methods are computationally
We discard terms of order δρ2 and higher, and so obtain
more efficient, though not necessary more accurate, than HF

∫
EXC [ ρ + δ ρ] = A (ρ 4 /3 + 43 ρ 1/3 δρ )dr methods.

∫
= EXC [ ρ] + 43 A ρ1/3δ ρdr

Therefore, the differential δE XC of the functional (the differ-

ence EXC[ρ + δρ] – EXC[ρ] that depends linearly on δρ) is Formulate form for the Formulate trial
exchange–correlation density, ρ
∫ 

VXC ( r )δρ dr
 energy, EXC[ρ] Electronic
δEXC [ρ ] = A ρ δρ dr
4
3 ∫ 1/3
Evaluate the
No Yes
energy, E,
eqn 30.2
exchange–correlation
and therefore potential, VXC, eqn 30.5
Convergence?
1/ 2
4 3 ⎛ 3⎞ Kohn–Sham
VXC (r ) = A ρ 1/3 = − ⎜ ⎟ j0 ρ(r )
1/3 (30.7) equations, eqn 30.4
3 2 ⎝ π⎠ Electron density,
Kohn–Sham ρ, eqn 30.3
Self-test 30.1 Find the exchange–correlation potential if the orbitals, ψ
exchange–correlation energy is given by EXC [ ρ] = B ∫ ρ(r )2 dr .
Answer: V XC(r) = 2Bρ(r) Figure 30.2 The iteration procedure for solving the Kohn–
Sham equations in density functional theory.

Example 30.2 Applying the DFT method

Demonstrate how to apply DFT to molecular hydrogen. GTOs), and write ρ(r) = |χA|2 + |χB|2 for each electron. For the
exchange–correlation energy, EXC, use the form appropriate to a
Method Begin by assuming that the electron density is a sum
uniform electron gas and the corresponding exchange–correla-
of atomic electron densities arising from the presence of elec-
tion potential derived in Example 30.1.
trons in the atomic orbitals χA and χB (which may be STOs or

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 30 Density functional theory  259

Answer The Kohn–Sham orbital for the molecule is a solution of ρ (r1 )ρ (r2 )
ρ(2) ∫
E [ρ ] = 2 ψ a (r )h1ψ a (r ) dr + j0 ∫r12
dr1dr2

∫
h1ψ a (1) + j0
r12
dτ 2ψ a (1) + 43 Aρ (1)1/3ψ a (1) = ε aψ a (1)
9⎛ 3⎞
1/2

− ⎜ ⎟
8 ⎝ π⎠ ∫
j0 ρ(r )4 /3 dr
Now insert the ρ(r1) and ρ(r2) we have assumed, ρ(r) = |χ A|2 +
|χ B|2, and solve this equation numerically for ψ a. Once we have where the first term is the sum of the energies of the two electrons
that orbital, we replace our original guess at the electron density in the field of the two nuclei, the second term is the electron–
by ρ(r) = |ψ a(r)|2. This density is then substituted back into the electron repulsion, and the final term includes the correction
Kohn–Sham equation to obtain an improved function ψa(r) and due to non-classical electron–electron effects.
the process repeated until the density and exchange–correlation
energy are unchanged to within a specified tolerance on succes- Self-test 30.2 What would the final term be if the exchange–
sive iterations. correlation potential were that deduced in Self-test 30.1?
When convergence of the iterations has been achieved, the Answer: B ∫ ρ(r )2 dr
electronic energy (eqn 30.2) is calculated from

Checklist of concepts
☐ 1. In density functional theory (DFT), the electronic
energy is written as a functional of the electron prob-
ability density.
☐ 2. The Hohenberg–Kohn theorem guarantees that the
exact ground-state energy of a molecule is uniquely
determined by the electron probability density.
☐ 3. The exchange–correlation energy takes into account
non-classical electron–electron effects.
☐ 4. The electron density is computed from the Kohn–Sham
orbitals, the solutions to the Kohn–Sham equations.
The latter equations are solved self-consistently.
☐ 5. The exchange–correlation potential is the functional
derivative of the exchange–correlation energy.
☐ 6. One commonly used but approximate form for the
exchange–correlation energy is based on the model of
an electron gas.

Checklist of equations
Property Equation Comment Equation number

Energy E[ρ] = Eclassical[ρ] + EXC[ρ] 30.2

Ne
Electron density ρ(r ) =
∑ |ψ (r)|
i =1
i
2 Definition 30.3

Kohn–Sham equations
∫
h1ψ i (1) + j0 ( ρ(2) / r12 )dτ 2ψ i (1) + VXC (1)ψ i (1) = ε iψ i (1) Solve numerically and iteratively 30.4

Exchange–correlation VXC (r ) = δ EXC [ρ]/δ ρ Definition; a functional derivative 30.5

potential

VXC (r ) = − 23 (3 /π)1/2 j0 ρ(r )1/3 Electron-gas model 30.7

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 260 6 Molecular structure
Focus 6 on Molecular structure
Topic 22 Valence-bond theory
Discussion questions
22.1 Discuss the role of the Born–Oppenheimer approximation in the
calculation of a molecular potential energy curve or surface.
22.2 Why are promotion and hybridization invoked in valence-bond theory?
22.3 Describe the various types of hybrid orbitals and how they are used
to describe the bonding in alkanes, alkenes, and alkynes. How does
hybridization explain that in allene, CH2 = C = CH2, the two CH2 groups lie in
perpendicular planes?
Exercises
22.1(a) Write the valence-bond wavefunction for the single bond in HF.
22.1(b) Write the valence-bond wavefunction for the triple bond in N2.
22.2(a) Write the valence-bond wavefunction for the resonance hybrid
HF ↔ H+F− ↔ H−F+ (allow for different contributions of each structure).
22.2(b) Write the valence-bond wavefunction for the resonance hybrid
N2 ↔ N+N− ↔ N2–N2+ ↔ structures of similar energy.
22.3(a) Describe the structure of a P2 molecule in valence-bond terms. Why is
P4 a more stable form of molecular phosphorus?
22.3(b) Describe the structures of SO2 and SO3 in terms of valence-bond
theory.
Problems
22.1 An sp2 hybrid orbital that lies in the xy plane and makes an angle of 120°
to the x-axis has the form
⎛ 22.3 Show that if two equivalent hybrid orbitals of the form spλ make an angle
1 1 31/2 ⎞
ψ= ⎜ s − 21/2 p x + 21/2 p y ⎟
31/2 ⎝ ⎠
Use hydrogenic atomic orbitals to write the explicit form of the hybrid orbital.
Show that it has its maximum amplitude in the direction specified.
Topic 23 The principles of molecular orbital theory
Discussion questions
23.1 What feature of molecular orbital theory is responsible for bond
formation?
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Atkins09819.indb 260
22.4 Why is spin pairing so common a feature of bond formation (in the
context of valence-bond theory)?
22.5 What are the consequences of resonance?
22.6 Write the Lewis structure of the peroxynitrite ion, ONOO−. Label each
atom with its state of hybridization and specify the composition of each of the
different types of bond.
22.4(a) Describe the bonding in 1,3-butadiene using hybrid orbitals.
22.4(b) Describe the bonding in 1,3-pentadiene using hybrid orbitals.
22.5(a) Show that the linear combinations h1 = s + px + py + pz and
h2 = s − px − py + pz are mutually orthogonal.
22.5(b) Show that the linear combinations h1 = (sin χ)s + (cos χ)p and
h2 = (cos χ)s – (sin χ)p are mutually orthogonal for all values of the angle χ.
22.6(a) Normalize the sp2 hybrid orbital h = s + 21/2p given that the s and
p orbitals are each normalized to 1.
22.6(b) Normalize the linear combinations in Exercise 22.5(b) given that the
s and p orbitals are each normalized to 1.
22.2 Confirm that the hybrid orbitals in eqn 22.7 make angles of 120° to each
other.
θ to each other, then λ = –1/cos θ. Plot a graph of λ against θ and confirm that
θ = 180° when λ = 1 and θ = 120° when λ = 2.
23.2 Why is spin pairing so common a feature of bond formation (in the
context of molecular orbital theory)?
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 Exercises and problems  261

Exercises
23.1(a) Normalize the molecular orbital ψ = ψA + λψB in terms of the energy curve and find the bond dissociation energy (in electronvolts) and the
parameter λ and the overlap integral S. equilibrium bond length.
23.1(b) A better description of the molecule in Exercise 23.1(a) might be
obtained by including more orbitals on each atom in the linear combination. R/a0 0 1 2 3 4
Normalize the molecular orbital ψ =ψ A + λψ B + λ ′ψ B′ in terms of the j/Eh 1.000 0.729 0.472 0.330 0.250
parameters λ and λ′ and the appropriate overlap integrals S, where ψB and ψ B′
are mutually orthogonal orbitals on atom B. k/Eh 1.000 0.736 0.406 0.199 0.092
S 1.000 0.858 0.587 0.349 0.189
23.2(a) Suppose that a molecular orbital has the (unnormalized) form
0.145A + 0.844B. Find a linear combination of the orbitals A and B that is
where Eh = 27.2 eV, a0 = 52.9 pm, and EH1s = − 12 Eh .
orthogonal to this combination and determine the normalization constants of
23.3(b) The same data as in Exercise 23.3(a) may be used to calculate the
both combinations using S = 0.250.
molecular potential energy curve for the antibonding orbital, which is given
23.2(b) Suppose that a molecular orbital has the (unnormalized) form
by eqn 23.7. Plot the curve.
0.727A + 0.144B. Find a linear combination of the orbitals A and B that is
orthogonal to this combination and determine the normalization constants of 23.4(a) Identify the g or u character of bonding and antibonding π orbitals
both combinations using S = 0.117. formed by side-by-side overlap of p atomic orbitals.
23.4(b) Identify the g or u character of bonding and antibonding δ orbitals
23.3(a) The energy of H2+ with internuclear separation R is given by eqn 23.4.
formed by face-to-face overlap of d atomic orbitals.
The values of the contributions are given below. Plot the molecular potential

Problems
23.1 Calculate the (molar) energy of electrostatic repulsion between two 23.5 ‡ The LCAO-MO approach described in the text can be used to introduce
hydrogen nuclei at the separation in H2 (74.1 pm). The result is the energy numerical methods needed in quantum chemistry. In this problem we
that must be overcome by the attraction from the electrons that form the evaluate the overlap, Coulomb, and resonance integrals numerically and
bond. Does the gravitational attraction between them play any significant compare the results with the analytical equations (eqns 23.5). (a) Use the
role? Hint: The gravitational potential energy of two masses is equal to LCAO-MO wavefunction and the H2+ hamiltonian to derive equations
–Gm1m2/r. for the relevant integrals, and use mathematical software or an electronic
spreadsheet to evaluate the overlap, Coulomb, and resonance integrals
23.2 Imagine a small electron-sensitive probe of volume 1.00 pm3 inserted into
numerically, and the total energy for the 1sσg MO in the range a0 < R < 4a0.
an H2+ molecule ion in its ground state. Calculate the probability that it will
Compare the results obtained by numerical integration with results obtained
register the presence of an electron at the following positions: (a) at nucleus A,
analytically. (b) Use the results of the numerical integrations to draw a graph
(b) at nucleus B, (c) halfway between A and B, (c) at a point 20 pm along the
of the total energy, E(R), and determine the minimum of total energy, the
bond from A and 10 pm perpendicularly. Do the same for the molecule ion the
equilibrium internuclear distance, and the dissociation energy (De).
instant after the electron has been excited into the antibonding LCAO-MO.
23.6(a) Calculate the total amplitude of the normalized bonding and
23.3 Derive eqns 23.4 and 23.7 by working with the normalized LCAO-MOs
antibonding LCAO-MOs that may be formed from two H1s orbitals at a
for the H2+ molecule-ion. Proceed by evaluating the expectation value of the
separation of 2a0 = 106 pm. Plot the two amplitudes for positions along the
hamiltonian for the ion. Make use of the fact that A and B each individually
molecular axis both inside and outside the internuclear region. (b) Plot the
satisfy the Schrödinger equation for an isolated H atom.
probability densities of the two orbitals. Then form the difference density, the
23.4 Examine whether occupation of the bonding orbital with one electron difference between ψ 2 and 12 (ψ A2 +ψ B2 ).
(as calculated in the preceding problem) has a greater or lesser bonding effect
than occupation of the antibonding orbital with one electron. Is that true at all
internuclear separations?

Topic 24 Homonuclear diatomic molecules

Discussion questions
24.1 Draw diagrams to show the various orientations in which a p orbital and
a d orbital on adjacent atoms may form bonding and antibonding molecular
orbitals.
24.2 Outline the rules of the building-up principle for homonuclear diatomic
molecules.
24.3 What is the role of the Born–Oppenheimer approximation in molecular
orbital theory?
24.4 What is the justification for treating s and p atomic-orbital contributions
to molecular orbitals separately?
24.5 To what extent can orbital overlap be related to bond strength?

‡ These problems were supplied by Charles Trapp and Carmen Giunta.

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 262 6 Molecular structure
Exercises
24.1(a) Give the ground-state electron configurations and bond orders of
(a) Li2, (b) Be2, and (c) C2.
24.1(b) Give the ground-state electron configurations of (a) F2− , (b) N2,
and (c) O2− 2 .
24.2(a) From the ground-state electron configurations of B2 and C2, predict
which molecule should have the greater bond dissociation energy.
24.2(b) From the ground-state electron configurations of Li2 and Be2, predict
which molecule should have the greater bond dissociation energy.
24.3(a) Which has the higher dissociation energy, F2 or F2+ ?
24.3(b) Arrange the species O2+ , O2, O2− , O2−
2 in order of increasing bond
length.
24.4(a) Evaluate the bond order of each Period 2 homonuclear diatomic.
24.4(b) Evaluate the bond order of each Period 2 homonuclear diatomic
cation, X 2+ , and anion, X 2− .
Problems
24.1 Sketch how the overlap between a 1s orbital and a 2p orbital directed
towards it can be expected to depend on their separation. The overlap integral
between an H1s orbital and an H2p orbital directed towards it on nuclei
separated by a distance R is S = (R/a0 ){1+ (R/a0 ) + 13 (R/a0 )2 }e − R/ao .
Plot this function, and find the separation for which the overlap is a
maximum.
24.2‡ Use the 2px and 2pz hydrogenic atomic orbitals to construct simple
LCAO descriptions of 2pσ and 2pπ molecular orbitals. (a) Make a
probability density plot, and both surface and contour plots of the xz-plane
amplitudes of the 2pzσ and 2pzσ* molecular orbitals. (b) Make surface and
contour plots of the xz-plane amplitudes of the 2pxπ and 2pxπ* molecular
orbitals. Include plots for both an internuclear distance, R, of 10a0 and 3a0,
where a0 = 52.9 pm. Interpret the graphs, and explain why this graphical
information is useful.
Topic 25 Heteronuclear diatomic molecules
Discussion questions
25.1 Describe the Pauling and Mulliken electronegativity scales. Why should
they be approximately in step?
25.2 Why do both ionization energy and electron affinity play a role in
estimating the energy of an atomic orbital to use in a molecular structure
calculation?
Exercises
25.1(a) Give the ground-state electron configurations of (a) CO, (b) NO, and
(c) CN−.
25.1(b) Give the ground-state electron configurations of (a) XeF, (b) PN, and
(c) SO−.
25.2(a) Sketch the molecular orbital energy level diagram for XeF and deduce
its ground-state electron configuration. Is XeF likely to have a shorter bond
length than XeF+?
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24.5(a) For each of the species in Exercise 24.3(b), specify which molecular
orbital is the HOMO.
24.5(b) For each of the species in Exercise 24.3(b), specify which molecular
orbital is the LUMO.
24.6(a) What is the speed of a photoelectron ejected from an orbital of
ionization energy 12.0 eV by a photon of radiation of wavelength 100 nm?
24.6(b) What is the speed of a photoelectron ejected from a molecule with
radiation of energy 21 eV and known to come from an orbital of ionization
energy 12 eV?
24.7(a) The overlap integral between two hydrogenic 1s orbitals on nuclei
separated by a distance R is given by eqn 24.4. At what separation is S = 0.20
for (i) H2, (ii) He2?
24.7(b) The overlap integral between two hydrogenic 2s orbitals on nuclei
separated by a distance R is given by the expression in Brief illustration 24.2.
At what separation is S = 0.20 for (i) H2, (ii) He2?
24.3 Show, if overlap is ignored, (a) that any molecular orbital expressed as
a linear combination of two atomic orbitals may be written in the form
ψ = ψA cos θ + ψB sin θ, where θ is a parameter that varies between 0 and 12 π,
and (b) that if ψA and ψB are orthogonal and normalized to 1, then ψ is also
normalized to 1. (c) To what values of θ do the bonding and antibonding
orbitals in a homonuclear diatomic molecule correspond?
24.4 In a particular photoelectron spectrum using 21.21 eV photons, electrons
were ejected with kinetic energies of 11.01 eV, 8.23 eV, and 5.22 eV. Sketch the
molecular orbital energy level diagram for the species, showing the ionization
energies of the three identifiable orbitals.
24.5 Show that overlap integral between two hydrogenic 2s orbitals is given by
⎪⎧ ZR 1 ⎛ ZR ⎞ 1 ⎛ ZR ⎞ ⎪⎫ − ZR/2a0
2 4
S(2s, 2s) = ⎨1+ + ⎜ +
2a0 12 ⎝ a0 ⎠ 240 ⎝ a0 ⎠ ⎬⎪
⎟ ⎜ ⎟ e
⎩⎪ ⎭
25.3 Discuss the steps involved in the calculation of the energy of a system by
using the variation principle. Are any assumptions involved?
25.4 What is the physical significance of the Coulomb and resonance integrals?
25.5 Discuss how the properties of carbon explain the bonding features that
make it an ideal biological building block.
25.2(b) Sketch the molecular orbital energy level diagram for IF and deduce its
ground-state electron configuration. Is IF likely to have a shorter bond length
than IF− or IF+?
25.3(a) Use the electron configurations of NO− and NO+ to predict which is
likely to have the shorter bond length.
25.3(b) Use the electron configurations of SO− and SO+ to predict which is
likely to have the shorter bond length.
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 Exercises and problems  263

25.4(a) A reasonably reliable conversion between the Mulliken and Pauling 25.5(b) Estimate the orbital energies to use in a calculation of the molecular
electronegativity scales is given by eqn 25.4. Use Table 25.1 to assess how good orbitals of HBr. For data, see Tables 20.2 and 20.3.
the conversion formula is for Period 2 elements.
25.6(a) Use the values derived in Exercise 25.5(a) to estimate the molecular
25.4(b) A reasonably reliable conversion between the Mulliken and Pauling
orbital energies in HCl; use S = 0.
electronegativity scales is given by eqn 25.4. Use Table 25.1 to assess how good
25.6(b) Use the values derived in Exercise 25.5(b) to estimate the molecular
the conversion formula is for Period 3 elements.
orbital energies in HBr; use S = 0.
25.5(a) Estimate the orbital energies to use in a calculation of the molecular
25.7(a) Now repeat Exercise 25.6(a), but with S = 0.20.
orbitals of HCl. For data, see Tables 20.2 and 20.3.
25.7(b) Now repeat Exercise 25.6(b), but with S = 0.20.

Problems
25.1 Equation 25.8c follows from eqn 25.8a by making the approximation
|αB – αA| >> 2|β| and setting S = 0. Explore the consequences of not setting
S = 0.
25.2 Suppose that a molecular orbital of a heteronuclear diatomic molecule is
built from the orbital basis A, B, and C, where B and C are both on one atom
(they can be envisaged as F2s and F2p in HF, for instance). Set up the secular
equations for the optimum values of the coefficients and the corresponding
secular determinant.
25.3 Continue the preceding problem by setting αA = –7.2 eV, αB = –10.4 eV,
αC = –8.4 eV, βAB = –1.0 eV, βAC = –0.8 eV, and calculate the orbital energies
and coefficients with (i) both S = 0, (ii) both S = 0.2.
25.4 As a variation of the preceding problem explore the consequences of
increasing the energy separation of the B and C orbitals (use S = 0 for this
stage of the calculation). Are you justified in ignoring orbital C at any stage?

Topic 26 Polyatomic molecules

Discussion questions
26.1 Discuss the scope, consequences, and limitations of the approximations 26.2 Distinguish between delocalization energy, π-electron binding energy,
on which the Hückel method is based. and π-bond formation energy. Explain how each concept is employed.

Exercises
26.1(a) Write down the secular determinants for (a) linear H3, (b) cyclic H3
within the Hückel approximation.
26.1(b) Write down the secular determinants for (a) linear H4, (b) cyclic H4
within the Hückel approximation.
26.2(a) Predict the electron configurations of (a) the benzene anion, (b) the
benzene cation. Estimate the π-electron binding energy in each case. 1 Anthracene 2 Phenanthrene
26.2(b) Predict the electron configurations of (a) the allyl radical, (b) the
cyclobutadiene cation. Estimate the π-electron binding energy in 26.4(b) Write down the secular determinants for (a) azulene (3),
each case. (b) acenaphthalene (4) within the Hückel approximation and using the C2p
26.3(a) Compute the delocalization energy and π-bond formation energy of
orbitals as the basis set.
(a) the benzene anion, (b) the benzene cation.
26.3(b) Compute the delocalization energy and π-bond formation energy of
(a) the allyl radical, (b) the cyclobutadiene cation.

3 Azulene 4 Acenaphthalene
26.4(a) Write down the secular determinants for (a) anthracene (1), (b)
26.5(a) Use mathematical software to estimate the π-electron binding energy
phenanthrene (2) within the Hückel approximation and using the C2p
of (a) anthracene (1), (b) phenanthrene (2) within the Hückel approximation.
orbitals as the basis set.
26.5(b) Use mathematical software to estimate the π-electron binding energy
of (a) azulene (3), (b) acenaphthalene (4) within the Hückel approximation.

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 264 6 Molecular structure
Problems
26.1 Set up and solve the Hückel secular equations for the π electrons of
3 . Express the energies in terms of the Coulomb integrals αO and αC and
CO2−
the resonance integral β. Determine the delocalization energy of the ion.
26.2 For a linear conjugated polyene with each of N carbon atoms contributing
an electron in a 2p orbital, the energies Ek of the resulting π molecular orbitals
are given by
kπ
Ek = α + 2 β cos k = 1, 2, 3, … N
N +1
(a) Use this expression to determine a reasonable empirical estimate of the
resonance integral β for the homologous series consisting of ethene, butadiene,
hexatriene, and octatetraene, given that π* ← π ultraviolet absorptions from
the HOMO to the LUMO occur at 61 500, 46 080, 39 750, and 32 900 cm−1,
respectively. (b) Calculate the π-electron delocalization energy, Edeloc = Eπ −
n(α + β), of octatetraene, where Eπ is the total π-electron binding energy and n
is the total number of π electrons. (c) In the context of this Hückel model, the π
molecular orbitals are written as linear combinations of the carbon 2p orbitals.
The coefficient of the jth atomic orbital in the kth molecular orbital is given by
1/2
⎛ 2 ⎞ jkπ
ckj = ⎜ sin j = 1, 2, 3, …, N
⎝ N +1 ⎠⎟ N +1
Determine the values of the coefficients of each of the six 2p orbitals in each
of the six π molecular orbitals of hexatriene. Match each set of coefficients
(that is, each molecular orbital) with a value of the energy calculated with the
expression given in part (a) of the molecular orbital. Comment on trends that
relate the energy of a molecular orbital with its ‘shape’, which can be inferred
from the magnitudes and signs of the coefficients in the linear combination
that describes the molecular orbital.
26.3 For monocyclic conjugated polyenes (such as cyclobutadiene and
benzene) with each of N carbon atoms contributing an electron in a 2p
orbital, simple Hückel theory gives the following expression for the energies
Ek of the resulting π molecular orbitals:
2k π
Ek = α + 2 β cos k = 0, ±1, …± N /2 for N even
N
k = 0, ±1, …± (N −1)/ 2 for N odd
(a) Calculate the energies of the π molecular orbitals of benzene and
cyclooctatetraene (5). Comment on the presence or absence of degenerate
energy levels. (b) Calculate and compare the delocalization energies of
benzene (using the expression above) and hexatriene. What do you conclude
from your results? (c) Calculate and compare the delocalization energies
of cyclooctatetraene and octatetraene. Are your conclusions for this pair of
molecules the same as for the pair of molecules investigated in part (b)?
5 Cyclooctatetraene
26.4 Set up the secular determinants for the homologous series consisting of
ethene, butadiene, hexatriene, and octatetraene and diagonalize them by using
mathematical software. Use your results to show that the π molecular orbitals
of linear polyenes obey the following rules:
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Atkins09819.indb 264
t

The π molecular orbital with lowest energy is delocalized over all carbon
atoms in the chain.
t

The number of nodal planes between C2p orbitals increases with the energy
of the π molecular orbital.
26.5 Set up the secular determinants for cyclobutadiene, benzene, and
cyclooctatetraene and diagonalize them by using mathematical software. Use
your results to show that the π molecular orbitals of monocyclic polyenes with
an even number of carbon atoms follow a pattern in which:
t
The π molecular orbitals of lowest and highest energy are non-degenerate.
t
The remaining π molecular orbitals exist as degenerate pairs.
26.6 Electronic excitation of a molecule may weaken or strengthen some
bonds because bonding and antibonding characteristics differ between the
HOMO and the LUMO. For example, a carbon–carbon bond in a linear
polyene may have bonding character in the HOMO and antibonding
character in the LUMO. Therefore, promotion of an electron from the HOMO
to the LUMO weakens this carbon–carbon bond in the excited electronic
state, relative to the ground electronic state. Consult Figs 26.2 and 26.4 and
discuss in detail any changes in bond order that accompany the π* ← π
ultraviolet absorptions in butadiene and benzene.
26.7‡ Prove that for an open chain of N conjugated carbons the characteristic
polynomial of the secular determinant (the polynomial obtained by
expanding the determinant), PN(x), where x = (α – β)/β, obeys the recurrence
relation PN = xPN – 1 – PN – 2, with P1 = x and P0 = 1.
26.8 The standard potential of an electrode is a measure of the thermodynamic
tendency of an atom, ion, or molecule to accept an electron (Topic 77).
Studies indicate that there is a correlation between the LUMO energy and
the standard potential of aromatic hydrocarbons. Do you expect the standard
potential to increase or decrease as the LUMO energy decreases? Explain your
answer.
26.9‡ In Exercise 26.1(a) you are invited to set up the Hückel secular
determinant for linear and cyclic H3. The same secular determinant applies
to the molecular ions H3+ and D3+ . The molecular ion H3+ was discovered
as long ago as 1912 by J.J. Thomson but its equilateral triangular structure
was confirmed by M.J. Gaillard, et al. much more recently (Phys. Rev. A17,
1797 (1978)). The molecular ion H3+ is the simplest polyatomic hydrogen
species with a confirmed existence and plays an important role in chemical
reactions occurring in interstellar clouds that may lead to the formation of
water, carbon monoxide, and ethanol. The H3+ ion has also been found in
the atmospheres of Jupiter, Saturn, and Uranus. (a) Solve the Hückel secular
equations for the energies of the H3 system in terms of the parameters α and
β, draw an energy level diagram for the orbitals, and determine the binding
energies of H3+ , H3, and H3− . (b) Accurate quantum mechanical calculations
by G.D. Carney and R.N. Porter (J. Chem. Phys. 65, 3547 (1976)) give the
dissociation energy for the process H3+ → H + H + H + as 849 kJ mol−1. From
this information and data in Table 24.2, calculate the enthalpy of the reaction
H + (g ) + H2 (g ) → H3+ (g ). (c) From your equations and the information given,
calculate a value for the resonance integral β in H3+ . Then go on to calculate
the binding energies of the other H3 species in (a).
26.10‡ There is some indication that other hydrogen ring compounds and
ions in addition to H3 and D3 species may play a role in interstellar chemistry.
According to J.S. Wright and G.A. DiLabio (J. Phys. Chem. 96, 10793 (1992)),
H5− , H6, and H7+ are particularly stable whereas H4 and H5+ are not. Confirm
these statements using Hückel calculations.
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Topic 27 Self-consistent fields
Discussion questions
27.1 Describe the physical significance of each of the terms that appears in the
Fock operator.
27.2 Outline the computational steps used in the Hartree–Fock self-consistent
field approach to electronic structure calculations.
27.3 Explain how the Roothaan equations arise in the Hartree–Fock method.
What additional approximations do they represent?
Exercises
27.1(a) Write the expression for the potential energy contribution to the
electronic hamiltonian for LiH.
27.1(b) Write the expression for the potential energy contribution to the
electronic hamiltonian for BeH2.
27.2(a) Write the electronic hamiltonian for HeH+.
27.2(b) Write the electronic hamiltonian for LiH2+.
27.3(a) Write the Slater determinant for the ground state of HeH+.
27.3(b) Write the Slater determinant for the ground state of LiH2+.
27.4(a) Write the Hartree–Fock equation for HeH+.
27.4(b) Write the Hartree–Fock equation for LiH2+.
27.5(a) Set up the Roothaan equations for HeH+ and establish the
simultaneous equations corresponding to the Roothaan equations. Adopt a
basis set of two real normalized functions, one centred on H and one on He;
denote the molecular orbitals by ψa and ψb.
27.5(b) Set up the Roothaan equations for LiH2+ and establish the
simultaneous equations corresponding to the Roothaan equations. Adopt a
basis set of two real normalized functions, one centred on H and one on Li;
denote the molecular orbitals by ψa and ψb.
27.6(a) Construct the elements FAA and FAB for the species HeH+ and express
them in terms of the notation in eqn 27.14.
27.6(b) Construct the elements FAA and FAB for the species LiH2+ and express
them in terms of the notation in eqn 27.14.
Problems
One of the following problems requires the use of commercially available
software. Use versions that are available with this text or the software
recommended by your instructor.
27.1 Using appropriate electronic structure software and basis sets of your
or your instructor’s choosing, perform Hartree–Fock self-consistent field
calculations for the ground electronic states of H2 and F2. Determine ground-
state energies and equilibrium geometries. Compare computed equilibrium
bond lengths to experimental values.
27.2 A useful property of determinants is that interchanging any two rows or
columns changes their sign and therefore that if any two rows or columns are
identical, then the determinant vanishes. Use this property to show that (a)
the wavefunction (expressed as a Slater determinant) is antisymmetric under
particle exchange, (b) no two electrons can occupy the same orbital with the
same spin.
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Exercises and problems  265
27.4 Explain why the use of Gaussian-type orbitals is generally preferred over
the use of Slater-type orbitals in basis sets.
27.5 Describe why the Slater determinant provides a useful representation of
electron configurations of many-electron atoms. Why is it an approximation
to the true wavefunction?
27.6 Discuss the role of basis-set functions in electronic structure calculations.
What are some commonly used basis sets?
27.7(a) Identify all of the four-centre, two-electron integrals that are equal to
(AA|AB).
27.7(b) Identify all of the four-centre, two-electron integrals that are equal to
(BB|BA).
27.8(a) How many basis functions are needed in an electronic structure
calculation on CH3Cl using a minimal basis set?
27.8(b) How many basis functions are needed in an electronic structure
calculation on CH2Cl2 using a minimal basis set?
27.9(a) What is the general mathematical form of a p-type Gaussian?
27.9(b) What is the general mathematical form of a d-type Gaussian?
27.10(a) A one-dimensional Gaussian (in x) has the form e−αx or x n e −αx ;
2 2
one-dimensional Gaussians in y and z have similar forms. Show that the
s-type Gaussian (see eqn 27.16) can be written as a product of three one-
dimensional Gaussians.
27.10(b) A one-dimensional Gaussian (in x) has the form e −αx or x n e −αx ;
2 2
one-dimensional Gaussians in y and z have similar forms. Show that a p-type
Gaussian (see eqn 27.16) can be written as a product of three one-dimensional
Gaussians.
27.11(a) Show that the product of s-type Gaussians on He and H in HeH+ is a
Gaussian at an intermediate position. Note that the Gaussians have different
exponents.
27.11(b) Show that the product of s-type Gaussians on Li and H in LiH2+ is a
Gaussian at an intermediate position. Note that the Gaussians have different
exponents.
27.3 Show that the Slater determinant in eqn 27.2a is normalized assuming
that the spinorbitals from which it is constructed are orthogonal and
normalized.
27.4 It is often necessary during the course of an electronic structure
calculation to take derivatives of the basis functions with respect to nuclear
coordinates. Show that the derivative of an s-type Gaussian with respect
to x yields a p-type Gaussian and that the derivative of a p-type Gaussian
(of the form x e −α r ) yields a sum of s- and d-type Gaussians (which are
2
proportional to functions such as e −αr and xye −α r and its analogues,
2 2
respectively).
27.5 Consider a four-centre integral in an electronic structure calculation on
NH3 involving s-type Gaussian functions centred on each atomic nucleus.
Show that the four-centre, two-electron integral reduces to an integral over
two different centres.
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 266 6 Molecular structure

27.6 (a) In a continuation of Exercise 27.5(a) for HeH+, proceed to determine 27.7 (a) Continuing the Hartree–Fock calculation on HeH+ in Problem
the energies of the two molecular orbitals as well as the relation between the 27.6(a), give the expressions for all four of the elements of the Fock matrix
two coefficients for ψa and the relation between the two coefficients for ψb.. in terms of four-centre, two-electron integrals; the latter are defined in eqn
(b) Repeat for LiH2+ (in a continuation of Exercise 27.5(b)). 27.14. (b) Repeat for LiH2+ (in a continuation of Problem 27.6(b).)

Topic 28 Semi-empirical methods

Discussion questions
28.1 Why is Hückel molecular orbital theory considered a semi-empirical 28.2 Describe some of the common semi-empirical methods.
method?

Exercises
28.1(a) Identify the quadratic equation for the coefficient of the basis function 28.2(a) Identify the two-electron integrals that are set to zero in the semi-
centred on H in HeH+ starting from the Fock matrix and making the Hückel empirical method known as (a) CNDO, (b) INDO.
approximations. 28.2(b) Identify the two-electron integrals that are set to zero in in the semi-
28.1(b) Identify the quadratic equation for the coefficient of the basis function empirical method known as NDDO.
centred on H in LiH2+ starting from the Fock matrix and making the Hückel
approximations.

Problems
Some of the following problems require the use of commercially available
software. Use versions that are available with this text or the software
recommended by your instructor.
28.1 Use an appropriate semi-empirical method to compute the equilibrium
bond lengths and standard enthalpies of formation of (a) ethanol, C2H5OH,
(b) 1,4-dichlorobenzene, C6H4Cl2. Compare to experimental values and
suggest reasons for any discrepancies.
28.2 Molecular electronic structure methods may be used to estimate the
standard enthalpy of formation of molecules in the gas phase. (a) Use a
semi-empirical method of your choice to calculate the standard enthalpies of
formation of ethene, butadiene, hexatriene, and octatetraene in the gas phase.
(b) Consult a database of thermochemical data, and, for each molecule in
part (a), calculate the difference between the calculated and experimental
values of the standard enthalpy of formation. (c) A good thermochemical
database will also report the uncertainty in the experimental value of the
standard enthalpy of formation. Compare experimental uncertainties
with the relative errors calculated in part (b) and discuss the reliability of
your chosen semi-empirical method for the estimation of thermochemical
properties of linear polyenes.
28.3 (a) Using the expressions for the four elements of the Fock matrix for
HeH+ determined in Problem 27.7(a), show how these expressions simplify if
the CNDO semi-empirical method is used. (b) Repeat for LiH2+, beginning
with the expressions determined in Problem 27.7(b).
28.4 (a) In a continuation of Problem 27.6(a), use Hückel molecular orbital
theory to express the energies of the molecular orbitals in terms of α and β.
(b) Repeat for LiH2+ (in a continuation of Problem 27.6(b)).

Topic 29 Ab initio methods

Discussion questions
29.1 Discuss what is meant by a virtual orbital, a singly excited determinant, 29.3 Describe the choice of the hamiltonians H  (1) in MPPT.
 (0) and H
and a doubly excited determinant.
29.4 Discuss the importance of Brillouin's theorem in electronic structure
29.2 Describe some computational limitations of the configuration interaction calculations.
method.

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Exercises
29.1(a) In a Hartree–Fock calculation on the silicon atom using 20 basis-set
functions, how many of the molecular orbitals generated would be unoccupied
and could be used as virtual orbitals in a configuration interaction calculation?
29.1(b) In a Hartree–Fock calculation on the sulfur atom using 20 basis-set
functions, how many of the molecular orbitals generated would be unoccupied
and could be used as virtual orbitals in a configuration interaction calculation?
29.2(a) Give an example of a singly excited determinant in a CI calculation of H2.
29.2(b) Give an example of a doubly excited determinant in a CI calculation of H2.
29.3(a) Use eqn 29.1 to write the expression for the ground-state wavefunction
in a CI calculation on HeH+ involving the ground-state determinant and a
singly excited determinant.
Problems
29.1‡ Luo, et al. (J. Chem. Phys. 98, 3564 (1993)) reported experimental
observation of He2, a species that had escaped detection for a long time. The
observation required temperatures in the neighbourhood of 1 mK. Perform
configuration interaction and MPPT electronic structure calculations and
compute the equilibrium bond length Re of the dimer as well as the energy
of the dimer at Re relative to the separated He + He atomic limit. (High-level,
accurate computational studies suggest that the well depth for He2 is about
0.0151 zJ at a distance Re of about 297 pm.)
29.2 In a configuration interaction calculation on the excited 3 Σ u+ electronic
state of H2, which of the following Slater determinants can contribute to the
excited-state wavefunction?
(a) 1σ gα 1σ uα (b) 1σ gα 1παu
(c) |1σ uα 1πβg | (d) 1σ gβ 2σ uβ
(e) 1παu 1παg (f) 1πβu 2πβu
29.3 Use MPPT to obtain an expression for the ground-state wavefunction
corrected to first order in the perturbation.
Topic 30 Density functional theory
Discussion questions
30.1 Describe some of the advantages of density functional theory compared
to other Hartree–Fock based methods.
30.2 Discuss what is meant by a ‘functional’.
Exercises
30.1(a) Which of the following are functionals? (a) d(x3)/dx; (b) d(x3)/dx
3
evaluated at x =1; (c) ∫ x 3dx ; (d) ∫1 x 3dx?
30.1(b) Which of the following are functionals? (a) d(3x2)/dx; (b) d(3x2)/dx
3 30.3(a) Write the two Kohn–Sham equations for the Kohn–Sham orbitals in a
evaluated at x = 4; (c) ∫3x2dx; (d) ∫1 3x 2 dx ?
30.2(a) Using eqn 30.3, write the expression for the electron density in terms of
the Kohn–Sham orbitals in a DFT calculation on LiH.
Atkins09819.indb 267
Exercises and problems  267
29.3(b) Use eqn 29.1 to write the expression for the ground-state wavefunction
in a CI calculation on LiH2+ involving the ground-state and a doubly excited
determinant.
29.4(a) The second-order energy correction (eqn 29.5) in MPPT arises from
the doubly excited determinant (the M = 2 term). Derive an expression for the
integral that appears in the numerator of eqn 29.5 in terms of the integrals
(AB|CD) for HeH+.
29.4(b) The second-order energy correction (eqn 29.5) in MPPT arises from
the doubly excited determinant (the M = 2 term). Derive an expression for the
integral that appears in the numerator of eqn 29.5 in terms of the integrals
(AB|CD) for LiH2+.
29.4 (a) Show why configuration interaction gives an improved ground-
state wavefunction for HeH+ compared to the Hartree–Fock ground-state
wavefunction. Use a minimal basis set and ignore overlap. Follow along
the lines of the argument presented in Brief illustration 29.1 but recognize
the complication introduced by the fact that HeH+ does not have inversion
symmetry. (b) Repeat for LiH2+.
29.5 In Example 29.1, the secular equation for a CI calculation on molecular
hydrogen using the ground-state Slater determinant and the doubly
excited determinant was presented as well as the expression for one of the
hamiltonian matrix elements. Develop similar expressions for the remaining
hamiltonian matrix elements.
29.6 Show that in MPPT first-order energy corrections do not contribute to
the correlation energy.
29.7 Prove Brillouin’s theorem, which states that the hamiltonian matrix
elements between the ground-state Hartree–Fock Slater determinant and
singly excited determinants are zero.
29.8 Derive an expression for the second-order estimate of the correlation
energy for H2 if, in a CI calculation using a minimal basis set, the overlap
between the two basis-set functions is not ignored but set equal to a constant S.
30.3 Describe the contributions to the energy functional E[ρ].
30.4 Discuss what is meant by a uniform electron gas and how it is used
in DFT.
30.2(b) Using eqn 30.3, write the expression for the electron density in terms
of the Kohn–Sham orbitals in a DFT calculation on BeH2.
DFT calculation on HeH+. Use the exchange–correlation potential of eqn 30.7.
30.3(b) Write the two Kohn–Sham equations for the Kohn–Sham orbitals in a
DFT calculation on LiH2+. Use the exchange–correlation potential of eqn 30.7.
9/11/2013 11:38:19 AM
 268 6 Molecular structure
Problem
30.1 Find the DFT exchange–correlation potential if the exchange–correlation
energy is given by ∫ C ρ 5/ 3dr .
Integrated activities
F6.1 State and compare the approximations on which the valence-bond and
molecular orbital theories are based.
F6.2 Use concepts of molecular orbital theory to describe the chemical
reactivity of O2, N2, and NO.
F6.3 Explain why the Hartree–Fock formalism does not account for electron
correlation but the methods of configuration interaction and many-body
perturbation theory do.
F6.4 Distinguish between semi-empirical, ab initio, and density functional
theory methods of electronic structure determination.
F6.5 Is DFT a semi-empirical method? Justify your answer.
F6.6 Which of the molecules N2, NO, O2, C2, F2, and CN would you expect to
be stabilized by (a) the addition of an electron to form AB−, (b) the removal of
an electron to form AB+?
F6.7 State the parities of the six π orbitals of benzene.
F6.8 The languages of valence-bond theory and molecular orbital theory are
commonly combined when discussing unsaturated organic compounds.
Construct the molecular orbital energy level diagram of ethene on the basis
that the molecule is formed from the appropriately hybridized CH2 or CH
fragments. Repeat for ethyne (acetylene).
F6.9 Molecular orbital calculations based on semi-empirical, ab initio, and
DFT methods describe the spectroscopic properties of conjugated molecules
better than simple Hückel theory. (a) Use the computational method of
your choice (semi-empirical, ab initio, or density functional) to calculate the
energy separation between the HOMO and LUMO of ethene, butadiene,
hexatriene, and octatetraene. (b) Plot the HOMO–LUMO energy separations
against the experimental frequencies for π* ← π ultraviolet absorptions for
these molecules (61 500, 46 080, 39 750, and 32 900 cm−1, respectively). Use
mathematical software to find the polynomial equation that best fits the data.
(b) Use your polynomial fit from part (b) to estimate the wavenumber and
wavelength of the π* ← π ultraviolet absorption of decapentaene from the
calculated HOMO–LUMO energy separation. (c) Discuss why the calibration
procedure of part (b) is necessary.
F6.10 Here we develop a molecular orbital theory treatment of the peptide
group (6), which links amino acids in proteins, and establish the features that
stabilize its planar conformation.
O
C R2
C N
H
6 Peptide group
(a) It will be familiar from introductory chemistry that valence-bond theory
explains the planar conformation by invoking delocalization of the π bond
over the oxygen, carbon, and nitrogen atoms by resonance:
–
O O
C + C
C N C N
H H
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Atkins09819.indb 268
It follows that we can model the peptide group using molecular orbital theory
by making LCAO-MOs from 2p orbitals perpendicular to the plane defined
by the O, C, and N atoms. The three combinations have the form
ψ 1 = aψ O + bψ C + cψ N ψ 2 = dψ O − eψ N ψ 3 = f ψ O − gψ C + hψ N
where the coefficients a to h are all positive. Sketch the orbitals ψ1, ψ2, and ψ3 and
characterize them as bonding, nonbonding, or antibonding molecular orbitals. In
a nonbonding molecular orbital, a pair of electrons resides in an orbital confined
largely to one atom and not appreciably involved in bond formation. (b) Show that
this treatment is consistent only with a planar conformation of the peptide link.
(c) Draw a diagram showing the relative energies of these molecular orbitals and
determine the occupancy of the orbitals. Hint: Convince yourself that there are
four electrons to be distributed among the molecular orbitals. (d) Now consider a
non-planar conformation of the peptide link, in which the O2p and C2p orbitals
are perpendicular to the plane defined by the O, C, and N atoms, but the N2p
orbital lies on that plane. The LCAO-MOs are given by
ψ 4 = aψ O + bψ C ψ 5 = eψ N ψ 6 = f ψ O − gψ C
Just as before, sketch these molecular orbitals and characterize them as bonding,
nonbonding, or antibonding. Also, draw an energy level diagram and determine
the occupancy of the orbitals. (e) Why is this arrangement of atomic orbitals
consistent with a non-planar conformation for the peptide link? (f) Does the
bonding MO associated with the planar conformation have the same energy as
the bonding MO associated with the non-planar conformation? If not, which
bonding MO is lower in energy? Repeat the analysis for the nonbonding and
antibonding molecular orbitals. (g) Use your results from parts (a)–(f) to
construct arguments that support the planar model for the peptide link.
F6.11 Molecular orbital calculations may be used to predict trends in the
standard potentials of conjugated molecules, such as the quinones and flavins
that are involved in biological electron transfer reactions. It is commonly
assumed that decreasing the energy of the LUMO enhances the ability of a
molecule to accept an electron into the LUMO, with an accompanying increase
in the value of the molecule's standard potential. Furthermore, a number of
studies indicate that there is a linear correlation between the LUMO energy
and the reduction potential of aromatic hydrocarbons. (a) The standard
potentials at pH = 7 for the one-electron reduction of methyl-substituted
1,4-benzoquinones (7) to their respective semiquinone radical anions are:
R3 R5 R6 E</V
H H H H 0.078
CH3 H H H 0.023
CH3 H CH3 H −0.067
CH3 CH3 CH3 H −0.165
CH3 CH3 CH3 CH3 −0.260
O
R6 R2
R5 R3
O
7
9/11/2013 11:38:24 AM

(a) Using the computational method of your choice (semi-empirical, ab
initio, or density functional theory), calculate ELUMO, the energy of the
LUMO of each substituted 1,4-benzoquinone, and plot ELUMO against E<. Do
your calculations support a linear relation between ELUMO and E<? (b) The
1,4-benzoquinone for which R2 = R3 = CH3 and R5 = R6 = OCH3 is a suitable
model of ubiquinone, a component of the respiratory electron-transport
chain. Determine ELUMO of this quinone and then use your results from
part (a) to estimate its standard potential. (c) The 1,4-benzoquinone for
which R2 = R3 = R5 = CH3 and R6 = H is a suitable model of plastoquinone, a
component of the photosynthetic electron-transport chain. Determine ELUMO
of this quinone and then use your results from part (a) to estimate its standard
potential. Is plastoquinone expected to be a better or worse oxidizing agent
than ubiquinone?
F6.12 Use appropriate electronic structure software and basis sets of your or
your instructor’s choosing to perform electronic structure calculations for the
ground electronic states of H2 and F2 using (a) MP2; (b) DFT; (c) CI including
ground-state, singly excited, and doubly excited Slater determinants.
Determine ground-state energies and equilibrium geometries. Compare
computed equilibrium bond lengths to experimental values.
F6.13 The variation principle can be used to formulate the wavefunctions
of electrons in atoms as well as molecules. Suppose that the function
ψ trial = N (α )e −α r , with N(α) the normalization constant and α an adjustable
2
parameter, is used as a trial wavefunction for the 1s orbital of the hydrogen
atom. Show that
1/2
3α
2 ⎛ 2α ⎞
E(α ) = − 2e 2 ⎜
2μ ⎝ π ⎟⎠
where e is the fundamental charge and μ is the reduced mass for the H atom.
What is the minimum energy associated with this trial wavefunction?
F6.14 In ‘free electron molecular orbital’ (FEMO) theory, the electrons in a
conjugated molecule are treated as independent particles in a box of length
Atkins09819.indb 269
Exercises and problems  269
L. Sketch the form of the two occupied orbitals in butadiene predicted by
this model and predict the minimum excitation energy of the molecule.
The conjugated tetraene CH2 = CHCH = CHCH = CHCH = CH2 can be
treated as a box of length 8R, where R ≈ 140 pm (as in this case, an extra
half bond-length is often added at each end of the box). Calculate the
minimum excitation energy of the molecule and sketch the HOMO and
LUMO. Estimate the colour a sample of the compound is likely to appear in
white light.
F6.15 An important quantity in nuclear magnetic resonance spectroscopy
(Topics 47 − 49) and which should be familiar from 13C-NMR spectra of
organic molecules, is the chemical shift; this experimentally determined
quantity is influenced by the details of the electronic structure near the 13C
nucleus of interest. Consider the following series of molecules: benzene,
methylbenzene, trifluoromethylbenzene, benzonitrile, and nitrobenzene in
which the substituents para to the C atom of interest are H, CH3, CF3, CN,
and NO2, respectively. (a) Use the computational method of your choice
to calculate the net charge at the C atom para to these substituents in the
series of organic molecules given above. (b) It is found empirically that the
13C chemical shift of the para C atom increases in the order: methylbenzene,
benzene, trifluoromethylbenzene, benzonitrile, nitrobenzene. Is there
a correlation between the behaviour of the 13C chemical shift and the
computed net charge on the 13C atom? (This problem is revisited in Focus 10,
Problem F10.1.)
F6.16 Use mathematical software, a spreadsheet, or the Living graphs (labelled
LG) on the website of this book for the following exercises:
(a) Plot the amplitude of the bonding molecular orbital in a hydrogen molecule-
ion in a plane containing the two nuclei for different values of the internuclear
distance. Point to the features of the 1σ orbital that lead to bonding.
(b) Plot the amplitude of the antibonding molecular orbital in a hydrogen
molecule-ion in a plane containing the two nuclei for different values of
the internuclear distance. Point to the features of the 2σ orbital that lead to
antibonding.
9/11/2013 11:38:26 AM
 270 Mathematical background 5

Mathematical background 5 Matrices

A matrix is an array of numbers that are generalizations of and a 3 × 3 determinant is evaluated by expanding it as a sum of
ordinary numbers. We shall consider only square matrices, 2 × 2 determinants:
which have the numbers arranged in the same number of rows
and columns. By using matrices, we can manipulate large num- a b c
e f d f d e
bers of ordinary numbers simultaneously. A determinant is a d e f =a −b +c 3×3
h i g i g h Deter- (MB5.3b)
particular combination of the numbers that appear in a matrix g h i
minant
and is used to manipulate the matrix. = a(ei − fh) − b(di − fg ) + c(dh − eg )
Matrices may be combined together by addition or multi-
plication according to generalizations of the rules for ordinary Note the sign change in alternate columns (b occurs with a
numbers. Although we describe below the key algebraic pro- negative sign in the expansion). An important property of
cedures involving matrices, it is important to note that most a determinant is that if any two rows or any two columns are
numerical matrix manipulations are now carried out with interchanged, then the determinant changes sign.
mathematical software. You are encouraged to use such soft-
ware, if it is available to you. Brief illustration MB5.1 Matrix manipulations

MB5.1 Definitions The following grid illustrates the features so far:

Consider a square matrix M of n2 numbers arranged in n col- Matrix Transpose Determinant

umns and n rows. These n2 numbers are the elements of the M MT |M|
matrix, and may be specified by stating the row, r, and column,
⎛ 1 2⎞ ⎛ 1 3⎞ 1 2
c, at which they occur. Each element is therefore denoted Mrc. ⎜ 3 4⎟ ⎜ 2 4⎟ = 1× 4 − 2 × 3 = −2
⎝ ⎠ ⎝ ⎠ 3 4
A diagonal matrix is a matrix in which the only nonzero ele-
ments lie on the major diagonal (the diagonal from M11 to
Mnn). Thus, the matrix

⎛ 1 0 0⎞
MB5.2 Matrix addition and multiplication
D = ⎜⎜ 0 2 0⎟⎟ Two matrices M and N may be added to give the sum S = M +
⎜⎝ 0 0 1⎟⎠ N, according to the rule

is a 3 × 3 diagonal square matrix. The condition may be written Src = Mrc + N rc Matrix addition (MB5.4)

Mrc = mr δ rc (MB5.1) That is, corresponding elements are added. Two matrices may also
be multiplied to give the product P = MN according to the rule
where δrc is the Kronecker delta, which is equal to 1 for r = c
and to 0 for r ≠ c. In the above example, m1 = 1, m2 = 2, and
m3 = 1. The unit matrix, 1 (and occasionally I), is a special case
Prc = ∑M
n
rn N nc Matrix multiplication (MB5.5)

of a diagonal matrix in which all nonzero elements are 1.

The transpose of a matrix M is denoted MT and is defined by These procedures are illustrated in Fig. MB5.1. It should be
noticed that in general MN ≠ NM, and matrix multiplication is
T
Mmn = Mnm Transpose (MB5.2) in general non-commutative (that is, it depends on the order of
multiplication).
That is, the element in row n, column m of the original matrix
becomes the element in row m, column n of the transpose (in Brief illustration MB5.2 Matrix addition and
effect, the elements are reflected across the diagonal). The deter- multiplication
minant, |M|, of the matrix M is a number arising from a specific
procedure for taking sums and differences of products of matrix Consider the matrices
elements. For example, a 2 × 2 determinant is evaluated as ⎛ 1 2⎞ ⎛ 5 6⎞
M =⎜ ⎟ and N = ⎜ ⎟
a b ⎝ 3 4⎠ ⎝ 7 8⎠
= ad − bc 2 × 2 Determinant (MB5.3a)
c d

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 Matrices  271

(column) matrix that satisfies the conditions of the eigenvalue

Their sum is
equation and has the form:
⎛ 1 2⎞ ⎛ 5 6⎞ ⎛ 6 8 ⎞
S=⎜ ⎟ +⎜ ⎟ =⎜ ⎟ ⎛ x1 ⎞
⎝ 3 4⎠ ⎝ 7 8⎠ ⎝ 10 12⎠
⎜x ⎟
x =⎜ ⎟
2
and their product is
⎜ ⎟
⎜ ⎟
⎛ 1 2⎞ ⎛ 5 6⎞ ⎛ 1 × 5 + 2 × 7 1 × 6 + 2 × 8 ⎞ ⎛ 19 22⎞ ⎝ xn ⎠
P =⎜ ⎟⎜ ⎟ =⎜ ⎟ =⎜ ⎟
⎝ 3 4⎠ ⎝ 7 8⎠ ⎝ 3 × 5 + 4 × 7 3 × 6 + 4 × 8⎠ ⎝ 43 50⎠
In general, there are n eigenvalues λ(i), i = 1, 2, …, n, and n cor-
responding eigenvectors x(i). We write eqn MB5.7a as (noting
that 1x = x)

+ + + ( M − λ1)x = 0 (MB5.7b)
+ = + + +
+ + + Equation MB5.7b has a solution only if the determinant |M –
(a) λ1| of the coefficients of the matrix M – λ1 is zero. It follows
that the n eigenvalues may be found from the solution of the
× + × + ... × + ... ... secular equation:
× = × + ... + ... ...
× M − λ1 = 0 (MB5.8)
... ... ...
(b) If the inverse of the matrix M – λ1 exists, then, from eqn
MB5.7b, (M – λ1)−1(M – λ1)x = x = 0, a trivial solution. For a
Figure MB5.1 A diagrammatic representation of (a) matrix nontrivial solution, (M – λ1)−1 must not exist, which is the case
addition, (b) matrix multiplication. if eqn MB5.8 holds.

The inverse of a matrix M is denoted M−1, and is defined so

that Brief illustration MB5.4 Simultaneous equations
MM = M M = 1
−1 −1
Inverse (MB5.6) Once again we use the matrix M in Brief illustration MB5.1,
and write eqn MB5.7 as
The inverse of a matrix is best constructed by using mathe-
matical software, and the tedious analytical approach is rarely ⎛ 1 2⎞ ⎛ x1 ⎞ ⎛ x1 ⎞ ⎛1− λ 2 ⎞ ⎛ x1 ⎞
necessary. ⎜ 3 4⎟ ⎜ x ⎟ = λ ⎜ x ⎟ rearranged into ⎜ 3 4 − λ ⎟⎠ ⎜⎝ x2 ⎟⎠
=0
⎝ ⎠ ⎝ 2⎠ ⎝ 2⎠ ⎝

Brief illustration MB5.3 Inversion From the rules of matrix multiplication, the latter form
expands into
Mathematical software gives the following inversion of M:
⎛ (1 − λ )x1 + 2 x2 ⎞
Matrix Inverse ⎜ 3 x + ( 4 − λ )x ⎟ = 0
⎝ 1 2⎠
M M−1
which is simply a statement of the two simultaneous equations
⎛ 1 2⎞ ⎛ −2 1 ⎞
⎜ 3 4⎟ ⎜ 3 1⎟ (1 − λ )x1 + 2 x2 = 0 and 3x1 + (4 − λ )x2 = 0
⎝ ⎠ ⎜ ⎟
⎝ 2 − 2⎠
The condition for these two equations to have solutions is

1− λ 2
M − λ1 = = (1 − λ )(4 − λ ) − 6 = 0
3 4−λ
MB5.3 Eigenvalue equations
An eigenvalue equation is an equation of the form This condition corresponds to the quadratic equation

λ 2 − 5λ − 2 = 0
Mx = λ x Eigenvalue equation (MB5.7a)
with solutions λ = +5.372 and λ = –0.372, the two eigenvalues
where M is a square matrix with n rows and n columns, λ is of the original equation.
a constant, the eigenvalue, and x is the eigenvector, an n × 1

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 272 Mathematical background 5

The n eigenvalues found by solving the secular equations are

which expands to
used to find the corresponding eigenvectors. To do so, we begin
by considering an n × n matrix X which will be formed from the ⎛ x1(1) + 2 x2(1) x1(2) + 2 x2(2) ⎞ ⎛ 5.372 x1(1) −0.372 x1(2) ⎞
eigenvectors corresponding to all the eigenvalues. Thus, if the ⎜ (1) =
(2) ⎟ ⎜ ⎟
⎝ 3x1 + 4 x2 3x1 + 4 x2 ⎠ ⎝ 5.372 x2 −0.372 x2(2) ⎠
(1) (2 ) (1)

eigenvalues are λ1, λ2, … and the corresponding eigenvectors

are This is a compact way of writing the four equations

⎛ x1(1) ⎞ ⎛ x1(2) ⎞ ⎛ x1(n) ⎞ x1(1) + 2 x2(1) = 5.372 x1(1) x1(2) + 2 x2(2) = −0.372 x1(2)
⎜ (1) ⎟ ⎜ (2) ⎟ ⎜ (n ) ⎟ 3x1(1) + 4 x2(1) = 5.372 x2(1) 3x1(2) + 4 x2(2) = − 0.372 x2(2)
x x x
x (1) = ⎜ 2 ⎟ x ( 2 ) = ⎜ 2 ⎟  x (n ) = ⎜ 2 ⎟
⎜  ⎟ ⎜  ⎟ ⎜  ⎟ corresponding to the two original simultaneous equations
⎜ (1) ⎟ ⎜ (2) ⎟ ⎜ (n ) ⎟
⎝ xn ⎠ ⎝ xn ⎠ ⎝ xn ⎠ and their two roots.
(MB5.9a)

the matrix X is Finally, we form X−1 from X and multiply eqn MB5.11 by it
from the left:
⎛ x1(1) x1(2)  x1(n) ⎞
⎜ (1) ⎟
x x2(2)  x2(n) ⎟ X −1 MX = X −1 X Λ = Λ
X = (x (1) x ( 2 )  x (n ) ) = ⎜ 2 (MB5.12)
⎜    ⎟
⎜ (1) ⎟ A structure of the form X−1MX is called a similarity trans-
⎝ xn xn(2)  xn(n) ⎠
(MB5.9b) formation. In this case the similarity transformation X−1MX
makes M diagonal (because Λ is diagonal). It follows that if
Similarly, we form an n × n matrix Λ with the eigenvalues λ the matrix X that causes X−1MX to be diagonal is known, then
along the diagonal and zeroes elsewhere: the problem is solved: the diagonal matrix so produced has the
eigenvalues as its only nonzero elements, and the matrix X used
⎛ λ1 0  0⎞
to bring about the transformation has the corresponding eigen-
⎜0 λ2  0 ⎟
Λ =⎜ ⎟ vectors as its columns. As will be appreciated once again, the
⎜  ⎟ solutions of eigenvalue equations are best found by using math-
⎜ ⎟
⎝0 0  λn ⎠ ematical software.
(MB5.10)

Brief illustration MB5.6 Similarity transformation

Now all the eigenvalue equations Mx(i) = λix(i) may be combined
into the single matrix equation To apply the similarity transformation, eqn MB5.12, to the
⎛ 1 2⎞
matrix from Brief illustration MB5.1 it is best to use
MX = X Λ ⎜ 3 4⎟
(MB5.11) ⎝ ⎠
mathematical software to find the form of X. The result is
⎛ 0.416 0.825 ⎞ ⎛ 0.574 0.837 ⎞
Brief illustration MB5.5 Eigenvalue equations X =⎜ X −1 = ⎜
⎟ ⎟
⎝ 0.909 −0.566⎠ ⎝ 0.922 −0.422⎠
⎛ 1 2⎞
In Brief illustration MB5.4 we established that if M = ⎜ ⎟
⎝ 3 4⎠ This result can be verified by carrying out the multiplication
⎛ x (1) ⎞ ⎛ 0.574 0.837 ⎞ ⎛ 1 2⎞ ⎛ 0.416 0.825 ⎞
then λ1 = +5.372 and λ2 = –0.372, with eigenvectors x (1) = ⎜ 1 ⎟ X −1MX = ⎜
(1)
⎝ x2 ⎠ ⎟⎜ ⎟⎜ ⎟
⎛ x1(2) ⎞ ⎝ 0.922 −0.422⎠ ⎝ 3 4⎠ ⎝ 0.909 −0.566⎠
and x (2) = ⎜ . We form
(2) ⎟ ⎛ 5.372 0 ⎞
⎝ x2 ⎠ =⎜
⎝ 0 −0 . 372⎟⎠
⎛ x1(1) x1(2) ⎞ ⎛ 5.372 0 ⎞
X = ⎜ (1) ⎟ Λ =⎜
⎝ x2 x2(2) ⎠ ⎝ 0 −0 . 372⎟⎠ The result is indeed the diagonal matrix Λ calculated in Brief
illustration MB5.4. It follows that the eigenvectors x(1) and x(2)
The expression MX = XΛ becomes are
⎛ 1 2⎞ ⎛ x1(1) x1(2) ⎞ ⎛ x1(1) x1(2) ⎞ ⎛ 5.372 0 ⎞ ⎛ 0.416⎞ ⎛ 0.825 ⎞
⎜ 3 4⎟ ⎜ x (1) ⎟ =⎜ (2) ⎟ ⎜ −0.372⎟⎠
x (1) = ⎜ ⎟ x (2) = ⎜ ⎟
⎝ ⎠⎝ 2 x2(2) ⎠ ⎝ x2(1) x2 ⎠ ⎝ 0 ⎝ 0.909⎠ ⎝ −0.566⎠

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 FOCUS 7 ON Molecular symmetry Focus 6

Molecular
Topic 31 Topic 32 Topic 33 structure
The analysis
Group Applications
of molecular
theory of
shape
symmetry
Focus 9

Molecular
spectroscopy

Many conclusions can be drawn without doing any calculation by taking note of the symmetry of
a molecule. Calculations too can be simplified by seeing that the symmetry of a molecule implies
that certain terms are necessarily zero. Symmetry arguments are used throughout the discussion of
Molecular structure and Molecular spectroscopy. They are also used in the description of the structures
of solids, but here we focus on individual molecules.
The first task is to identify the symmetries of a molecule (Topic 31). To do so, we introduce the
concepts of ‘symmetry operation’ and ‘symmetry element’. On doing so, we find that molecules can
be classified according to the symmetries they possess and put into one of a number of symmetry
groups. This classification is the first step in the application of symmetry arguments to molecules. We
show that some conclusions about molecular properties (such as the existence of polarity and chiral-
ity) can be drawn directly from the group to which the molecule belongs.
The next stage is to realize that the symmetry operations obey the same relations that mathemati-
cians use to define a ‘group’, and thus the study of symmetry is seen to be a part of ‘group theory’
(Topic 32). The recognition that symmetry is a part of group theory takes on great power when we
show that symmetry operations can be represented by numbers (more specifically, matrices, arrays
of numbers), for then the study of symmetry becomes quantitative. For most purposes in chemistry,
the ‘character table’ is the most useful, and the concept is introduced in this Topic.
The calculation of molecular properties often depends on the existence of certain integrals: group
theory provides powerful ways to conclude when these integrals necessarily vanish (Topic 33). It also
provides ways to decide which atomic orbitals can contribute to the molecular orbitals discussed in
the topics covered in Molecular structure.

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 TOPIC 31

The analysis of molecular shape

Some objects are ‘more symmetrical’ than others. A sphere is
Contents
more symmetrical than a cube because it looks the same after it
31.1 Symmetry operations and symmetry elements 275 has been rotated through any angle about any diameter. A cube
Brief illustration 31.1: Symmetry elements 276 looks the same only if it is rotated through certain angles about
31.2 The symmetry classification of molecules 276 specific axes, such as 90°, 180°, or 270° about an axis passing
Brief illustration 31.2: Symmetry classification 277 through the centres of any of its opposite faces (Fig. 31.1), or by
(a) The groups C1, Ci, and Cs 278 120° or 240° about an axis passing through any of its opposite
Brief illustration 31.3: C1, Ci, and Cs 278 corners. Similarly, an NH3 molecule is ‘more symmetrical’ than
(b) The groups Cn, Cnv, and Cnh 278 an H2O molecule because NH3 looks the same after rotations
Brief illustration 31.4: Cn, Cnv, and Cnh 278 of 120° or 240° about the axis shown in Fig. 31.2, whereas H2O
(c) The groups Dn, Dnh, and Dnd 279 looks the same only after a rotation of 180°.
Brief illustration 31.5: Dn, Dnh, and Dnd 279 This Topic puts these intuitive notions on a more for-
(d) The group Sn 279 mal foundation. In it, we see that molecules can be grouped
Brief illustration 31.6: Sn 280 together according to their symmetry, with the tetrahedral
(e) The cubic groups 280 species CH4 and SO2− 4 in one group and the pyramidal species
Brief illustration 31.7: The cubic groups 280
(f ) The full rotation group 281 C2
C3
31.3 Some immediate consequences of symmetry 281
(a) Polarity 281
Brief illustration 31.8: Polar molecules 281
(b) Chirality 281 C4
Brief illustration 31.9: Chiral molecules 282
Checklist of concepts 282

➤ Why do you need to know this material? Figure 31.1 Some of the symmetry elements of a cube. The
twofold, threefold, and fourfold axes are labelled with the
Symmetry arguments can be used to make immediate
conventional symbols.
assessments of the properties of molecules, and when
expressed quantitatively (Topic 32) can be used to save a
great deal of calculation. C3 C2

➤ What is the key idea?

Molecules can be classified into groups according to their
symmetry elements.

➤ What do you need to know already?

This Topic does not draw on others directly, but it will be
(a) (b)
useful to be aware of the shapes of a variety of simple
molecules and ions encountered in introductory chemistry Figure 31.2 (a) An NH3 molecule has a threefold (C3) axis and
courses. (b) an H2O molecule has a twofold (C2) axis. Both have other
symmetry elements too.

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NH3 and SO2− 3 in another. It turns out that molecules in the
same group share certain physical properties, so powerful pre-
dictions can be made about whole series of molecules once we
know the group to which they belong.
We have slipped in the term ‘group’ in its conventional sense.
In fact, a group in mathematics has a precise formal signifi-
cance and considerable power and gives rise to the name ‘group
theory’ for the quantitative study of symmetry. This power is
revealed in Topics 32 and 33.
Symmetry operations and
31.1
symmetry elements
An action that leaves an object looking the same after it has
been carried out is called a symmetry operation. Typical sym-
metry operations include rotations, reflections, and inversions.
There is a corresponding symmetry element for each symme-
try operation, which is the point, line, or plane with respect to
which the symmetry operation is performed. For instance, a
rotation (a symmetry operation) is carried out around an axis
(the corresponding symmetry element). We shall see that we
can classify molecules by identifying all their symmetry ele-
ments and grouping together molecules that possess the same
set of symmetry elements. This procedure, for example, puts
the trigonal pyramidal species NH3 and SO2− 3 into one group
and the angular species H2O and SO2 into another group.
In the following paragraphs we describe the operations and
the corresponding elements; for convenience, they are col-
lected in Table 31.1.
An n-fold rotation (the operation) about an n-fold axis
of symmetry, Cn (the corresponding element), is a rotation
through 360°/n. An H2O molecule has one twofold axis, C2.
An NH3 molecule has one threefold axis, C3, with which is
associated two symmetry operations, one being 120° rotation
in a clockwise sense and the other 120° rotation in an anti-
clockwise sense. There is only one twofold rotation associated
with a C2 axis because clockwise and anticlockwise 180° rota-
tions are identical. A pentagon has a C5 axis, with two rotations
(one clockwise, the other anticlockwise) through 72° associ-
ated with it. It also has an axis denoted C 52, corresponding to
two successive C5 rotations; there are two such operations, one
Table 31.1 Symmetry operations and symmetry elements
Symmetry operation Symbol Symmetry element
n-fold rotation Cn n-fold axis of rotation
Reflection σ Mirror plane
Inversion i Centre of symmetry
n-fold improper rotation Sn n-fold improper rotation axis
Identity E Entire object
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31 The analysis of molecular shape  275
through144° in a clockwise sense and the other through 144° in
an anticlockwise sense. A cube has three C4 axes, four C3 axes,
and six C2 axes. However, even this high symmetry is exceeded
by a sphere, which possesses an infinite number of symmetry
axes (along any diameter) of all possible integral values of n.
If a molecule possesses several rotation axes, then the one (or
more) with the greatest value of n is called the principal axis.
The principal axis of a benzene molecule is the sixfold axis per-
pendicular to the hexagonal ring (1).
C6
1 Benzene, C6H6
A reflection (the operation) in a mirror plane, σ (the ele-
ment), may contain the principal axis of a molecule or be
perpendicular to it. If the plane contains the principal axis, it
is called ‘vertical’ and denoted σv. An H2O molecule has two
vertical planes of symmetry (Fig. 31.3) and an NH3 molecule
has three. A vertical mirror plane that bisects the angle between
two C2 axes is called a ‘dihedral plane’ and is denoted σd (Fig.
31.4). When the plane of symmetry is perpendicular to the
principal axis it is called ‘horizontal’ and denoted σh. A C6H6
molecule has a C6 principal axis and a horizontal mirror plane
(as well as several other symmetry elements).
σv′
σv
Figure 31.3 An H2O molecule has two mirror planes. They are
both vertical (that is, contain the principal axis), so are denoted
σv and σ v′.
σd σd σd
Figure 31.4 Dihedral mirror planes (σd) bisect the C2 axes
perpendicular to the principal axis.
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 276 7 Molecular symmetry

F
Centre of
inversion, i C
I Cl

Br

2 CBrClFI

Figure 31.5 A regular octahedron has a centre of

inversion (i).

Brief illustration 31.1 Symmetry elements

In an inversion (the operation) through a centre of sym-
metry, i (the element), we imagine taking each point in a mol-
ecule, moving it to the centre of the molecule, and then moving
it out the same distance on the other side; that is, the point (x, y,
z) is taken into the point (−x, −y, −z). Neither an H2O molecule
nor an NH3 molecule has a centre of inversion, but a sphere
and a cube do have one. A C6H6 molecule does have a centre of
inversion, and so does a regular octahedron (Fig. 31.5); a regu-
lar tetrahedron and a CH4 molecule do not.
An n-fold improper rotation (the operation) about an
n-fold axis of improper rotation or an n-fold improper rota-
tion axis, Sn (the symmetry element), is composed of two
successive transformations. The first component is a rotation
through 360°/n, and the second is a reflection through a plane
perpendicular to the axis of that rotation. A CH4 molecule has
three S4 axes (Fig. 31.6).
The identity, E, consists of doing nothing; the corresponding
symmetry element is the entire object. Because every molecule
To identify the symmetry elements of a naphthalene molecule
(3) we first note that, like all molecules, it has the identity ele-
ment, E. There is one twofold axis of rotation, C2, perpendicu-
lar to the plane and two others, C2′, lying in the plane. There is
a mirror plane in the plane of the molecule, σ h, and two per-
pendicular planes, σv, containing the C2 rotation axis. There is
also a centre of inversion, i, at the midpoint of the molecule.
Note that some of these elements are implied by others: the
centre of inversion, for instance, is implied by the joint pres-
ence of a σv plane and a C2′ axis.
C2 σv
σv
i C2’
σh

is indistinguishable from itself if nothing is done to it, every

C2’
object possesses at least the identity element. One reason for
including the identity is that some molecules have only this
symmetry element (2).
3 Naphthalene, C10H8

Self-test 31.1 Identify the symmetry elements of an SF 6

S4 S6 molecule.
C4 Answer: E, 3S 4, 3C 4, 6C2, 4S6, 4C3, 3σh, 6σ d, i
C6
σh
σh

The symmetry classification

31.2

(a) (b)
Figure 31.6 (a) A CH4 molecule has a fourfold improper
rotation axis (S4): the molecule is indistinguishable after a 90°
rotation followed by a reflection across the horizontal plane,
but neither operation alone is a symmetry operation. (b) The
staggered form of ethane has an S6 axis composed of a 60°
rotation followed by a reflection.
of molecules
The classification of objects according to symmetry elements
corresponding to operations that leave at least one common
point unchanged gives rise to the point groups. There are five
kinds of symmetry operation (and five kinds of symmetry ele-
ment) of this kind (see Table 31.1). When we consider crys-
tals (Topic 37), we meet symmetries arising from translation

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 31 The analysis of molecular shape  277

Table 31.2 The notation for point groups through space. These more extensive groups are called space
groups.
Ci 1
To classify molecules according to their symmetries, we list
Cs m their symmetry elements and collect together molecules with
C1 1 C2 2 C3 3 C4 4 C6 6 the same list of elements. The name of the group to which a
C2v 2mm C3v 3m C4v 4mm C6v 6mm molecule belongs is determined by the symmetry elements it
C2h 2/m C3h 6 C4h 4/m C6h 6/m
possesses. There are two systems of notation (Table 31.2). The
Schoenflies system (in which a name looks like C4v) is more
D2 222 D3 32 D4 422 D6 622
common for the discussion of individual molecules, and the
D2h mmm D3h 62m D4h 4/mmm D6h 6/mmm Hermann–Mauguin system or International system (in which
D2d 42m D3d 3m S4 4/m S6 3 a name looks like 4mm) is used almost exclusively in the dis-
cussion of crystal symmetry. The identification of a molecule’s
T 23 Td 43m Th m3
point group according to the Schoenflies system is simplified
O 432 Oh m3m by referring to the flow diagram in Fig. 31.7 and the shapes
In the International system (or Hermann–Mauguin system) for point groups, a shown in Fig. 31.8.
number n denotes the presence of an n-fold axis and m denotes a mirror plane. A
slash (/) indicates that the mirror plane is perpendicular to the symmetry axis. It is
important to distinguish symmetry elements of the same type but of different n= 2 3 4 5 6 ∞
classes, as in 4/mmm, in which there are three classes of mirror plane. A bar over a
number indicates that the element is combined with an inversion. The only groups
listed here are the so-called ‘crystallographic point groups’. Cn

Molecule

Y N Two or
Linear? more Cnv
Cn, n > 2? Pyramid Cone

Y N C Y
D∞h i? ∞v Cnh
N
Y N
i?
Dnh
Plane or bipyramid
Y C5? N O Td
Ih h
Dnd
Select Cn with the highest n;
then, are there nC2 Y
perpendicular to Cn? Cn?
Y S2n
N N
Dnh Y σh?
Y
Cs σ?
N
N Figure 31.8 A summary of the shapes corresponding to
Dnd Y nσd?
N D
n
Y N C different point groups. The group to which a molecule belongs
Ci i? 1
can often be identified from this diagram without going
Y σ h? through the formal procedure in Fig. 31.7.
Cnh

N
Y Brief illustration 31.2 Symmetry classification
Cnv nσv?
To identify the point group to which a ruthenocene molecule
N
(4) belongs we use the flow diagram in Fig. 31.7. The path to
S2n Y N C
S2n? n trace is shown by a blue line; it ends at Dnh. Because the mol-
ecule has a fivefold axis, it belongs to the group D5h. If the rings
were staggered, as they are in an excited state of ferrocene
Figure 31.7 A flow diagram for determining the point group of
that lies 4 kJ mol−1 above the ground state (5), the horizontal
a molecule. Start at the top and answer the question posed in
each diamond (Y = yes, N = no).

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 278 7 Molecular symmetry

reflection plane would be absent, but dihedral planes would (b) The groups Cn, Cnv, and Cnh
be present.
A molecule belongs to the group Cn if it possesses an n-fold axis.
Cp = C5H5 Note that symbol Cn is now playing a triple role: as the label of
a symmetry element, a symmetry operation, and a group. If in
Cp = C5H5
addition to the identity and a Cn axis a molecule has n verti-
Ru Fe cal mirror planes σv, then it belongs to the group Cnv. Objects
that in addition to the identity and an n-fold principal axis also
have a horizontal mirror plane σh belong to the group Cnh. The
presence of certain symmetry elements Name Elements
5 Ferrocene, Fe(Cp)2 may be implied by the presence of oth-
4 Ruthenocene, Ru(Cp)2 Cn E, Cn
(excited state) ers: thus, in C2h the elements C2 and σh
Cnv E, Cn, nσv
jointly imply the presence of a centre of
Self-test 31.2 Classify the pentagonal antiprismatic excited Cnh E, Cn, σh
inversion (Fig. 31.9).
state of ferrocene (5).
Answer: D5d

C2

(a) The groups C1, Ci, and Cs

A molecule belongs to the group C1 if it has Name Elements i
no element other than the identity. It belongs C1 E
to Ci if it has the identity and the inversion σh
Ci E, i
alone, and to Cs if it has the identity and a
Cs E, σ
mirror plane alone.

Brief illustration 31.3 Figure 31.9 The presence of a twofold axis and a horizontal
C1, Ci, and Cs
mirror plane jointly imply the presence of a centre of inversion
The CBrClFI molecule (2) has only the identity element, and so in the molecule.
belongs to the group C1. meso-Tartaric acid (6) has the identity
and inversion elements, and so belongs to the group Ci. Quinoline Brief illustration 31.4 Cn, Cnv, and Cnh
(7) has the elements (E, σ), and so belongs to the group Cs.
An H2O2 molecule (9) has the symmetry elements E and C2, so
it belongs to the group C2. An H2O molecule has the symme-
COOH
O
try elements E, C2, and 2σv, so it belongs to the group C2v. An
OH
H Centre of NH3 molecule has the elements E, C3, and 3σv, so it belongs to
inversion the group C3v. A heteronuclear diatomic molecule such as HCl
H O
OH belongs to the group C ∞v because rotations around the axis by
any angle and reflections in all the infinite number of planes
COOH
COO H N that contain the axis are symmetry operations. Other mem-
bers of the group C ∞v include the linear OCS molecule and a
6 Meso-tartaric acid,
7 Quinoline, C9H7N cone. The molecule trans-CHClaCHCl (10) has the elements
HOOCCH(OH)CH(OH)COOH
E, C2, and σh, so belongs to the group C2h.
Self-test 31.3 Identify the group to which the molecule (8) belongs. σh
Cl

C2 C2
O

H Cl
8
9 Hydrogen peroxide, H2O2 10 trans-CHCl=CHCl
Answer: C2v

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 31 The analysis of molecular shape  279

Self-test 31.4 Identify the group to which the molecule B(OH)3 C3

in the conformation shown in (11) belongs. Cl

σh
C2
OH
C2
P
C3
B σh
C2

13 Phosphorus pentachloride, PCl5 (D

D3h)

11 B(OH)3
.
Answer: C3h C2’ C2’

(c) The groups Dn, Dnh, and Dnd

We see from Fig. 31.7 that a molecule that has an n-fold prin- C2, S4
cipal axis and n twofold axes perpendicular to Cn belongs to
the group Dn. A molecule belongs to Dnh if it also possesses a
horizontal mirror plane. D∞h is also 14 Allene, C3H4 (D
D2d)
Name Elements the group of the linear OCO and
Dn E , Cn , nC2′ HCCH molecules and of a uniform Self-test 31.5 Ident i f y t he g roups to wh ich (a) t he
cylinder. A molecule belongs to the tetrachloridoaurate(III) ion (15) and (b) the staggered confor-
Dnh E , Cn , nC2′ , σ h
group Dnd if in addition to the ele- mation of ethane (16) belong.
Dnd E , Cn , nC2′ , nσ d ments of Dn it possesses n dihedral
mirror planes σd. C2
C2

Cl
–
Brief illustration 31.5 Dn, Dnh, and Dnd C4
The planar trigonal BF3 molecule has the elements E, C3, 3C2, C2
Au C2
and σh (with one C2 axis along each B–F bond), so it belongs to
D3h (12). The C6H6 molecule has the elements E, C6, 3C2, 3C2′ , σh C3,S
S6
and σ h together with some others that these elements imply, σd
so it belongs to D6h. Three of the C2 axes bisect C–C bonds and
the other three pass through vertices of the hexagon formed by 15 Tetrac
T hloridoaurate(III) ion,
[AuCl4]– 16 Ethane, C2H6
the carbon framework of the molecule, and the prime on 3C2′
indicates that the three C 2 axes are different from the other
three C2 axes. All homonuclear diatomic molecules, such as Answer: (a) D4h, (b) D3d
N2 , belong to the group D ∞h because all rotations around the
axis are symmetry operations, as are end-to-end rotation and
end-to-end ref lection. Another example of a Dnh species is
(13). The twisted, 90° allene (14) belongs to D2d.

F (d) The group Sn

Molecules that have not been classified into one of the
B groups mentioned so far, but which possess one Sn axis, belong
to the group Sn. Note that
the group S2 is the same as Name Elements

12 Boron trifluoride, BF3

Ci, so such a molecule will Sn E, Sn, and groups
already have been classified not previously
classified
as Ci.

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 280 7 Molecular symmetry

Brief illustration 31.6 The group Th is based on T but also contains a centre of inver-
Sn
sion (Fig. 31.12).
Tetraphenylmethane belongs to the point group S 4 (17).
Molecules belonging to Sn with n > 4 are rare.

Ph

Ph
S4
Ph
Ph (a) (b) (c)

Figure 31.10 (a) Tetrahedral, (b) octahedral, and (c) icosahedral

17 Tetraphen
T ylmethane, C(C6H5)4 (S
S4)
molecules are drawn in a way that shows their relation
to a cube: they belong to the cubic groups Td, Oh, and Ih,
Self-test 31.6 Identify the group to which the ion in (18) respectively.
belongs.
S4
+

(a) (b)

Figure 31.11 Shapes corresponding to the point groups (a)

18 N(CH2CH(CH3)CH(CH3)CH2)2+
T and (b) O. The presence of the decorated slabs reduces the
symmetry of the object from Td and Oh, respectively.
Answer: S 4

(e) The cubic groups

A number of very important molecules possess more than one
principal axis. Most belong to the cubic groups and in particu-
lar to the tetrahedral groups T, Td, and Th (Fig. 31.10a) or to
the octahedral groups O and Oh (Fig. 31.10b). A few icosahe-
dral (20-faced) molecules belonging to the icosahedral group,
I (Fig. 31.10c), are also known. The groups Td and Oh are the
groups of the regular tetrahedron and the regular octahedron,
Figure 31.12 The shape of an object belonging to the group Th.
respectively. If the
object possesses the Name Elements
rotational symmetry T E, 4C3, 3C2 Brief illustration 31.7 The cubic groups
of the tetrahedron Td E, 3C2, 4C3, 3S4, 6σd
or the octahedron, Th The molecules CH4 and SF6 belong, respectively, to the groups
E, 3C2, 4C3, i, 4S6, 3σh
but none of their O Td and Oh . Molecules belonging to the icosahedral group I
E, 3C4, 4C3, 6C2
planes of reflection, include some of the boranes and buckminsterfullerene, C 60
Oh E, 3S4, 3C4, 6C2, 4S6, 4C3, 3σh, 6σd, i (19). The shapes shown in Fig. 31.11 belong to the groups T and
then it belongs to
the simpler groups
I E, 6C5, 10C3, 15C2 O, respectively.
T or O (Fig. 31.11). Ih E, 6S10, 10S6, 6C5, 10C3, 15C2, 15σ, i

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19 Buckminsterfullerene, C60 (I)
Self-test 31.7 Identify the group to which the object shown in
20 belongs.
20
Answer: Th
(f) The full rotation group
The full rotation group, R3 (the 3 refers to rotation in three
dimensions), consists of an infinite number of rotation axes
with all possible values of n. A sphere and an atom belong to
R3, but no molecule does. Exploring the consequences of R3 is a
very important way of applying sym-
Name Elements
metry arguments to atoms, and is an
R3 E, ∞C2, ∞C3, … alternative approach to the theory of
orbital angular momentum.
31.3Some immediate consequences
of symmetry
Some statements about the properties of a molecule can be
made as soon as its point group has been identified.
(a) Polarity
A polar molecule is one with a permanent electric dipole
moment (HCl, O3, and NH3 are examples). If the molecule
belongs to the group Cn with n > 1, it cannot possess a charge
distribution with a dipole moment perpendicular to the sym-
metry axis because the symmetry of the molecule implies that
any dipole that exists in one direction perpendicular to the axis
Atkins09819.indb 281
31 The analysis of molecular shape  281
(a) (b)
Figure 31.13 (a) A molecule with a Cn axis cannot have a dipole
perpendicular to the axis, but (b) it may have one parallel to
the axis. The arrows represent local contributions to the overall
electric dipole, such as may arise from bonds between pairs of
neighbouring atoms with different electronegativities.
is cancelled by an opposing dipole (Fig. 31.13a). For example,
the perpendicular component of the dipole associated with one
O–H bond in H2O is cancelled by an equal but opposite com-
ponent of the dipole of the second O–H bond, so any dipole
that the molecule has must be parallel to the twofold symmetry
axis. However, as the group makes no reference to operations
relating the two ends of the molecule, a charge distribution may
exist that results in a dipole along the axis (Fig. 31.13b), and
H2O has a dipole moment parallel to its twofold symmetry axis.
The same remarks apply generally to the group Cnv, so mol-
ecules belonging to any of the Cnv groups may be polar. In
all the other groups, such as C3h, D, etc., there are symmetry
operations that take one end of the molecule into the other.
Therefore, as well as having no dipole perpendicular to the axis,
such molecules can have none along the axis, for otherwise
these additional operations would not be symmetry operations.
We can conclude that only molecules belonging to the groups Cn,
Cnv, and Cs may have a permanent electric dipole moment. For
Cn and Cnv, that dipole moment must lie along the symmetry
axis.
Brief illustration 31.8 Polar molecules
Ozone, O3, which is angular and belongs to the group C2v, may
be polar (and is), but carbon dioxide, CO2, which is linear and
belongs to the group D ∞h, is not.
Self-test 31.8 Is tetraphenylmethane polar?
Answer: No (S 4)
(b) Chirality
A chiral molecule (from the Greek word for ‘hand’) is a mol-
ecule that cannot be superimposed on its mirror image. An
achiral molecule is a molecule that can be superimposed on its
mirror image. Chiral molecules are optically active in the sense
that they rotate the plane of polarized light. A chiral molecule
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 282 7 Molecular symmetry

Brief illustration 31.9 Chiral molecules

S2
A molecule may be chiral if it does not have a centre of inver-
sion or a mirror plane, which is the case with the amino acid
alanine (21), but not with glycine (22). However, a molecule
i
may be achiral even though it does not have a centre of inver-
sion. For example, the S 4 species (18) is achiral and optically
inactive: though it lacks i (that is, S2) it does have an S4 axis.

COOH
Figure 31.14 Some symmetry elements are implied by the
other symmetry elements in a group. Any molecule containing H
an inversion also possesses at least an S2 element because i and
S2 are equivalent.
NH2
CH3
and its mirror-image partner constitute an enantiomeric pair
21 L-Alanine, NH2CH(CH3)COOH
of isomers and rotate the plane of polarization in equal but
opposite directions.
A molecule may be chiral, and therefore optically active, only if
it does not possess an axis of improper rotation, Sn. We need to be COO
OH
aware that an Sn improper rotation axis may be present under a
different name, and be implied by other symmetry elements that
H
are present. For example, molecules belonging to the groups Cnh
possess an Sn axis implicitly because they possess both Cn and H N 2
NH
σh, which are the two components of an improper rotation axis.
Any molecule containing a centre of inversion, i, also possesses
22 Glycine, NH2CH2COOH
an S2 axis, because i is equivalent to C2 in conjunction with σh,
and that combination of elements is S2 (Fig.  31.14). It follows
that all molecules with centres of inversion are achiral and Self-test 31.9 Is tetraphenylmethane chiral?
hence optically inactive. Similarly, because S1 = σ, it follows that Answer: No (S 4)
any molecule with a mirror plane is achiral.

Checklist of concepts
☐ 1. A symmetry operation is an action that leaves an object
looking the same after it has been carried out; see Table
31.1.
☐ 2. A symmetry element is a point, line, or plane with
respect to which a symmetry operation is performed;
see Table 31.1.
☐ 3. The notation for point groups commonly used for mol-
ecules and solids is summarized in Table 31.2.
☐ 4. To be polar, a molecule must belong to Cn, Cnv, or C s
(and have no higher symmetry).
☐ 5. A molecule may be chiral only if it does not possess an
axis of improper rotation, Sn.

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 TOPIC 32

Group theory

Contents ➤ What do you need to know already?

32.1 The elements of group theory
Example 32.1: Showing that symmetry operations
form a group
Brief illustration 32.1: Classes
32.2 Matrix representations
(a) Representatives of operations
Brief illustration 32.2: Representatives
(b) The representation of a group
Brief illustration 32.3: Matrix representations
(c) Irreducible representations
Example 32.2: Reducing a representation
(d) Characters and symmetry species
Brief illustration 32.4: Symmetry species
32.3 Character tables
(a) Character tables and orbital degeneracy
Example 32.3: Using a character table to
judge degeneracy
(b) The symmetry species of atomic orbitals
Brief illustration 32.5: Symmetry species of
atomic orbitals
(c) The symmetry species of linear combinations
of orbitals
Example 32.4: Identifying the symmetry species
of orbitals
Checklist of concepts
Checklist of equations
➤ Why do you need to know this material?
Group theory puts qualitative ideas about symmetry on to
a systematic basis that can be applied to a wide variety of
calculations; it is used to draw conclusions that might not
be immediately obvious and as a result can greatly simplify
calculations. It is also the basis of the labelling of atomic
and molecular orbitals that is used throughout chemistry.
➤ What is the key idea?
Symmetry operations may be represented by the effect of
matrices acting on a basis.
283 You need to know about the types of symmetry operation
and element introduced in Topic 31. This discussion draws
284 heavily on matrix algebra, especially matrix multiplication,
284 as set out in Mathematical background 5.
285
285
285 The systematic discussion of symmetry is called group theory.
285 Much of group theory is a summary of common sense about the
285 symmetries of objects. However, because group theory is sys-
286 tematic, its rules can be applied in a straightforward, mechanical
286 way. In most cases the theory gives a simple, direct method for
286 arriving at useful conclusions with the minimum of calculation,
287 and this is the aspect we stress here. In some cases, though, they
287 lead to unexpected results.
287
288 32.1 The elements of group theory
288
A group in mathematics is a collection of transformations that
288 satisfy four criteria. Thus, if we write the transformations as
R, R′, … (which we can think of as reflections, rotations, and
289 so on, of the kind introduced in Topic 31), then they form a
group if:
290
290 1. One of the transformations is the identity (that is: ‘do
290 nothing’).
2. For every transformation R, the inverse transformation
R−1 is included in the collection so that the combination
RR−1 (the transformation R−1 followed by R) is equivalent
to the identity.
3. The combination RR′ (the transformation R′ followed by
R) is equivalent to a single member of the collection of
transformations.
4. The combination R(R′R″), the transformation (R′R″)
followed by R, is equivalent to (RR′)R″, the
transformation R″ followed by (RR′).
There is one potentially very confusing point that needs to be
clarified at the outset. The entities that make up a group are
its ‘elements’. In chemistry, these elements are almost always

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