SPECTROSCOPY AND QUANTUM CHEMISTRY

QUIM-3514
Dr. Jhon Zapata Rivera
Assistant Professor
Department of Chemistry

e-Mail: j.zapatar@uniandes.edu.co
Of ce: Block Q, Floor 8th, of ce 825
Attention: Wednesday, 11:00-13:00

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 THE CHEMICAL BOND IN DIATOMIC MOLECULES

• The Simplest One-Electron Molecule: H2+

• The Electronic Structure of Many-Electron Molecules

• Homonuclear Diatomic Molecules

• Bond Order, Bond Energy, and Bond Length

• Heteronuclear Diatomic Molecules

• Molecular Orbital Theory of Polyatomic Molecules

Bibliography:
1. Atkins P., Friedman R., “Molecular Quantum Mechanics". 5th Edition, Ed. Oxford University
Press Inc., New York, 2011.
2. Pauling L., Wilson Jr E. B., “Introduction to Quantum Mechanics with Applications to
Chemistry", Ed. Dover Publications Inc., New York, 1985.
3. Engel, T.; Hehre, W. J., Quantum Chemistry and Spectroscopy. Pearson Education, Inc. 2013.
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 The Simplest One-Electron Molecule: H2+
We begin by setting up the electronic Schrödinger equation for H2+ molecule in the Born–
Oppenheimer approximation, for which the Schrödinger equation can be solved exactly.

The two protons and the electron are shown at one instant in
time. The quantities R , ra , and rb represent the distances
between the charged particles.

2 2 2 2
̂ ℏ 2 e 1 e 1 e 1
H=− ∇e − − +
2me 4πε0 ra 4πε0 rb 4πε0 R

The rst term is the electron kinetic energy, the second and third terms are the attractive
Coulombic interaction between the electron and each of the nuclei.
The last term is the nuclear–nuclear repulsion, such as the eigenvalues for the electronic
Schrödinger equation Ĥ eψe = Eeψe are related to the total energy eigenvalues by
ZaZbe2
Etotal = Ee +
4πε0 Rab
The resulting solutions, the wave functions of Schrödinger equation, are called molecular
orbitals (MOs) and resemble atomic orbitals (AO) but spread over both nuclei.
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 The Simplest One-Electron Molecule: H2+
The solution of the Schrödinger equation for H2+ is so complicated that there can be little
hope that exact solutions will be found for more complicated molecules.
We approach H2+ wave function using the Linear Combination of AO (LCAO) model, which
gives insight into chemical bonding, and can be extended easily to many-electron molecules.
Inspection of the form of the wave functions for H2+, as depicted below, suggests that they
can be simulated by forming linear combinations of hydrogen atomic orbitals:
ψ+ ≈ ϕa + ϕb ψ− ≈ ϕa − ϕb

Contour diagrams of the (a) bonding and (b) anti-

bonding orbitals (1σ and 1σ*, respectively) of the
hydrogen molecule-ion.

where ϕa is a 1s orbital on nucleus Ha and ϕb its analogue on nucleus Hb:

3/2

π ( a0 )
1 ζ
ϕ1s = e −ζr/a0

For ψ+ , the accumulation of internuclear electron density is simulated by the constructive

interference that takes place between the two waves centered on neighboring atoms.
The nodal plane in the true wave function ψ− is recreated by the destructive interference
between waves superimposed with opposite signs.
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 The Simplest One-Electron Molecule: H2+
The partial justi cation for simulating molecular orbitals as an LCAO can be appreciated by
examining the Hamiltonian for H2+.
When the electron is close to nucleus A , ra < < rb , and hence the Hamiltonian is
approximately
2 2 2
̂ ℏ 2 e 1 e 1
H=− ∇e − +
2me 4πε0 ra 4πε0 R

Apart from the nal constant term, this Hamiltonian is the same as that for a hydrogen
atom.Then, close to nucleus A, the wave function of the electron resembles an 1s AO.
The same is true close to B , and this form of the solution is captured by the two linear
combinations constructed:
ψ+ = cg(ϕa + ϕb) and ψ− = cu(ϕa − ϕb)

The same conclusions can be reached in a more formal way by writing the molecular orbitals
as the following LCAO:
∑ r r
ψ= cϕ
r

The atomic orbitals used in this expansion constitute the basis set for the calculation.
In principle, we should use an in nite basis set for a precise recreation of the molecular
orbital, but in practice only a nite basis set is used.
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 The Simplest One-Electron Molecule: H2+
The optimum values of the coef cients of the basis set functions are found by applying the
variation method, which means that we have to solve the secular equations

⟨ψr | Ĥ | ψs⟩
E= ≥ ET
⟨ψr | ψs⟩

which means that we have to solve the secular equations

∑
cr(Hrs − ESrs) = 0
r

where Hrs is a matrix element of the Hamiltonian and Srs is an overlap matrix element:

Hrs = ⟨ϕr | Ĥ | ϕs⟩ and Srs = ⟨ϕr | ϕs⟩

These secular equations have non-trivial solutions only if the secular determinant vanishes.
We write this condition as

| H − ES | = 0

where H is the matrix of elements Hrs and S is the corresponding matrix of elements Srs.
To nd the roots of the determinant | H − ES | we need to evaluate the relevant matrix
elements.
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 The Simplest One-Electron Molecule: H2+
We consider a minimal basis set for H2+ composed of two atomic orbitals, one on hydrogen
atom A and the other on hydrogen atom B.

The secular determinant is 2 × 2 and, since the basis set functions are normalized and real,
we can write
Saa = Sbb = 1 and Sab = Sba = S

where S is the overlap integral, and

Haa = Hbb = α and Hab = Hba = β

where α is the molecular Coulomb integral and β is the resonance integral. The secular
determinant is therefore
α − E β − ES
=0
β − ES α − E
α+β α−β
and its roots are E+ = and E− =
1+S 1−S
The corresponding values for the real coef cients of the normalized wave functions are
1 1
ca = with cb =
(2(1 + S))1/2 (2(1 − S))1/2
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 The Simplest One-Electron Molecule: H2+
We insert the explicit form of the Hamiltonian into the de nition of the Coulomb integral α:
2 2 2
̂ e 1 e 1 e 1
α = ⟨ϕa | H | ϕa⟩ = E1s − ⟨ϕa | | ϕa⟩ + = E1s − j′ +
4πε0 rb 4πε0 R 4πε0 R
The second term corresponds to the total Coulombic energy of interaction between an
electron density ϕa2 and the second nucleus B. We call this contribution j′.

The interpretation of the integral j′ as the total Coulombic potential

energy arising from a charge distribution on A with nucleus B.

For the resonance integral β, we use the fact that ϕb is an eigenfunction of the Hamiltonian
for hydrogen atom B with eigenvalue E1s, and write

( 4πε0 R )
2 2 2
̂ e 1 e 1 e 1
β = ⟨ϕa | H | ϕb⟩ = E1s⟨ϕa | ϕb⟩ − ⟨ϕa | | ϕb⟩ + ⟨ϕa | ϕb⟩ = E1s + S − k′
4πε0 ra 4πε0 R

The interpretation of the integral k′ as the interaction of an overlap

charge distribution with one of the nuclei.

The integral k′ has no classical analogue. However, an indication of its signi cance is the
interaction of the overlap charge density, −eϕaϕb.



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 The Simplest One-Electron Molecule: H2+
The energies of the two LCAO-MOs for H2+ are:

e2 1 j′ + k′ e2 1 j′ − k′
E+ = E1s + − E− = E1s + −
4πε0 R 1 + S 4πε0 R 1 − S

The integrals j′ and k′ are both positive, with j′ > k′; the lower of the two energies is E+.

The molecular orbital energy level diagram of the hydrogen

molecule-ion in the LCAO approximation.
Note that the ψ− orbital is slightly more anti-bonding than
the ψ+orbital is bonding.

The ladder of energy levels is called a molecular orbital energy level diagram.
The lower-energy orbital is called a bonding orbital and the higher-energy orbital is called an
anti-bonding orbital.
Occupation of a bonding orbital lowers the energy of a molecule and helps to draw the two
nuclei together.
When an anti-bonding orbital is occupied, the energy of the molecule is raised and the two
nuclei tend to be forced apart.
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 The Simplest One-Electron Molecule: H2+
The wave functions in term of the two LCAO-MOs for H2+ are:

1
ψ+ = (ϕa + ϕb) bonding orbital
(2(1 + S)) 1/2

1
ψ− = (ϕa − ϕb) antibonding orbital
(2(1 − S)) 1/2

The two molecular orbitals can be classi ed according to their parity: their symmetry
properties under inversion of the electron coordinates.

The parity allows the classi cation of orbitals in a homonuclear diatomic

molecule as g and u.
a) Under inversion ψ+(x, y, z) = ψ+(−x, − y, − z) remaining indistinguishable
from itself, and hence it is classi ed as having gerade symmetry, denoted g.
b) In contrast, ψ−(x, y, z) = − ψ−(−x, − y, − z) changing it sign under
inversion, so it is classi ed as ungerade, and denoted u.

The full-dress versions of the orbital labels are therefore 1σg and 1σu .
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 The Electronic Structure of Many-Electron Molecules
In the model of electronic structure of H2, the orbital description is therefore ψ+(1)ψ+(2)
(con guration 1σg2), where the 1 and 2 in parentheses are the locations of the two electrons.
Writing the true wave function ψ(1,2) as a product ψ+(1)ψ+(2) is an approximation that is
valid only if electron–electron repulsion is ignored. In words, the approximation is valid if:

ℏ2 2 ℏ2 2 j0 j0 j0 j0 j0 j0 j0
H=− ∇1 − ∇2 − − − − + + ≈ H1 + H2 +
2me 2me ra1 ra1 ra2 rb2 r12 RAB RAB

where each Hi is expressed in terms of the coordinates of the electron i alone. The
approximate spatial wave function ψ+(1)ψ+(2) is symmetric under particle interchange.
Hence, the spin component must be proportional to α(1)β(2) − β(1)α(2) to guarantee that
the overall wave function is anti-symmetrical.
The full form of the two-electron approximate wave function for the ground state of
molecular hydrogen is
ψ(1,2) = ψ+(1)ψ+(2)σ−(1,2)

where the factor σ− is the normalized spin contribution σ−(1,2) = ( 12 )1/2(α(1)β(2) − β(1)α(2)).
Therefore, when the two electrons enter the single molecular orbital ψ+ , they do so with
paired spins (↑↓).
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 The Electronic Structure of Many-Electron Molecules
The energy of the molecule in found by evaluating the expectation value of the Hamiltonian.
The resulting expression is
j0 2j′ + 2k′ j + 2k + m + 4l
E = 2E1s + − +
R 1+S 2(1 + S)2
The sum of the rst three terms is identical to the energy of the hydrogen molecule-ion but
with two 1s-electrons. In addition to the integrals already de ned (S, j′ and k′), we need:
The repulsion of a charge density of electron 1 on hydrogen atom A with the charge density
of electron 2 on hydrogen atom B:
1
∫
2
j = j0 ϕA(1) ϕB(2)2 dτ1dτ2 = ⟨AB | AB⟩
r12
The repulsion of the overlap charge density of electron 1 and the overlap charge density of
electron 2: 1
∫
k = j0 ϕA(1)ϕB(1) ϕA(2)ϕB(2) dτ1dτ2 = ⟨AA | BB⟩
r12

The repulsion of the charge density of electron 1 on A with the overlap charge density of
electron 2: 1
∫
l = j0 ϕA(1)2 ϕA(2)ϕB(2) dτ1dτ2 = ⟨AA | AB⟩
r12

The repulsion of the charge density of electron 1 on A with the charge density of electron 2
also on A:
2 1
∫
2
m = j0 ϕA(1) ϕA(2) dτ1dτ2 = ⟨AA | AA⟩
r12
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 Homonuclear Diatomic Molecules
All MOs for homonuclear diatomics can be divided into two groups with regard to each of
two symmetry operations. All diatomic MOs have either σ or π and either g or u symmetry.

The rst of these is rotation along the z axis. If this rotation leaves the MO unchanged, it has
no nodes that contain this axis, and the MO has σ symmetry.

If the MO has one nodal plane containing the molecular axis, the MO has π symmetry.
Combining px or py AOs always gives rise to π MOs if the AOs have a common nodal plane.

Contour plots of several bonding and anti-

bonding orbitals of H2.
Positive and negative amplitudes are shown as
red and blue respectively.
Darker colors indicate larger values for the
magnitude of the amplitude.
The green arrows show the transformation
(x, y, z) → (−x, − y, − z) for each orbital.

The second operation is inversion through the center of the molecule. Placing the origin at
the center of the molecule:
If inversion corresponds to ψ(x, y, z) → ψ(−x, − y, − z), the MO has g symmetry.
If ψ(x, y, z) → − ψ(−x, − y, − z), the MO has u symmetry.
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 Homonuclear Diatomic Molecules
The contour plots of the rst few H2 MOs, including only the major AO in each case
(neglecting the s-p mixing), are:

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 Homonuclear Diatomic Molecules
The interaction of 1s orbitals on each atom gives rise to a bonding and an anti-bonding MO.
Each MO can hold two electrons of opposite spin.

The con gurations for H2 and He2 are (1σg) and (1σg)2(1σ* )2
u , respectively. The diagram looks:

Once the MO energy levels have been calculated, a molecular con guration is obtained by
putting two electrons in each MO, in order of increasing orbital energy, until all electrons
have been accommodated.
If the degeneracy of an energy level is greater than one, Hund’s rst rule is followed and the
electrons are placed in the MOs in such a way that the total number of unpaired electrons is
maximized. 15
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 Homonuclear Diatomic Molecules
Schematic MO energy diagram for the valence electrons in F2 (minor contributions due to
s-p mixing have been neglected):

The degenerate π and p orbitals are shown

slightly offset in energy.
The dominant atomic orbital contributions to
the MOs are shown as solid lines.

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 Homonuclear Diatomic Molecules
Schematic MO energy diagram for the valence electrons in N2 (lesser contributions arising
from s-p mixing are shown as dashed lines):

The degenerate π and p orbitals are shown

slightly offset in energy.
The dominant atomic orbital contributions to
the MOs are shown as solid lines.

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 Homonuclear Diatomic Molecules
On the basis of this discussion of H2, He2, N2, and F2, the MO formalism is extended to all
rst and second row homonuclear diatomic molecules.

Molecular orbital energy levels for occupied

MOs of the second row diatomics.
The 1σg and 1σ* u orbitals lie at much lower
values of energy and are not shown.

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 Bond Order, Bond Energy, and Bond Length
We introduce the concept of bond order, which is de ned as

Total Bonding Electrons − Total Antibonding Electrons

Bond Order =
2

We expect the bond energy to be very small for a bond order of zero and to increase with
increasing bond order.

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 Bond Order, Bond Energy, and Bond Length
Example Problem 1:
Arrange the following in terms of increasing bond energy and bond length on the basis of
their bond order: N2+, N2, N2-, and N22-.
The ground-state con gurations for these species are:

N2+ : (1σg)2(1σ*
u )2
(2σg ) 2
(2σ*
u ) 2
(1πu ) 2
(1πu ) 2
(3σg ) 1

N2 : (1σg)2(1σ*
u )2
(2σg ) 2
(2σ*
u ) 2
(1πu ) 2
(1πu ) 2
(3σg ) 2

N2− : (1σg)2(1σ*
u )2
(2σg )2
(2σ*
u ) 2
(1πu ) 2
(1πu ) 2
(3σg ) 2
(1π*
g ) 1

N22− : (1σg)2(1σ*
u ) 2
(2σg ) 2
(2σ*
u ) 2
(1πu ) 2
(1πu ) 2
(3σg ) 2
(1π*
g ) 1
(1π*
g ) 1

In this series, the bond order is 2.5, 3, 2.5, and 2.

Therefore, the bond energy is predicted to follow the order N2 > N2+, N2− > N22− using the
bond order alone.
−
However, because of the extra electron in the antibonding 1π*
g MO, the bond energy in N2
will be less than that in N2+.
Because bond lengths decrease as the bond strength increases, the bond length will follow
the opposite order.
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 Heteronuclear Diatomic Molecules
Let us consider ϕ1 be a hydrogen 1s orbital and ϕ2 a uorine 2pz orbital in the molecule HF.
The bonding and antibonding MOs have the form:
ψ1 = c1H ϕH1s + c1F ϕF2pz and ψ2 = c2H ϕH1s + c2F ϕF2pz

where the coef cients are to be determined. The MOs labeled 1 and 2 are the in-phase and
out-of-phase combinations of the AOs, respectively. Normalization requires that

(c1H )2 + (c1F )2 + 2c1H c1F SHF = 1 and (c2H )2 + (c2F )2 + 2c2H c2F SHF = 1

To calculate ε1, ε2, c1H, c2H, c1F, and c2F, we need numerical values for HHH, HFF, HHF, and SHF. To a
good approximation, HHH and HFF correspond to the rst ionization energies of H and F,
respectively.
Fitting experimental data gives the approximate empirical relation HHF = -1.75·SHF(HHHHFF)1/2.
We assume that SHF = 0.30, HHH = -13.6 eV, and HFF = -18.6 eV, so that HHF = -8.35 eV.
Substituting these values gives the MO energy levels shown next:

ε1 = − 19.6 eV for ψ1 = 0.34ϕH1s + 0.84ϕF2pz

ε2 = − 10.3 eV for ψ2 = 0.99ϕH1s − 0.63ϕF2pz

Note that the magnitudes of the coef cients in the MOs are not equal.
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 Heteronuclear Diatomic Molecules
The coef cient of the lower energy AO has the larger magnitude in the bonding MO and the
smaller magnitude in the antibonding MO.

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 Molecular Orbital Theory of Polyatomic Molecules
Erich Hückel formulated a useful application of qualitative MO theory to calculate the energy
levels of the delocalized p electrons in conjugated and aromatic molecules.
In the Hückel theory, the p atomic orbitals that combine to form π MOs are treated
separately from the sp 2 σ-bonded carbon backbone.
For the four-carbon π network in 1,3-butadiene, the π MO can be written in the form:

ψπ = c1ϕ2pz1 + c2ϕ2pz2 + c3ϕ2pz3 + c4ϕ2pz4

The variational method is used to calculate the coef cients that give the lowest energy for
the four MOs that result from combining four AOs. We obtain the following secular
equations:
c1(H11 − εS11) + c2(H12 − εS12) + c3(H13 − εS13) + c4(H14 − εS14) = 0

c1(H21 − εS21) + c2(H22 − εS22) + c3(H23 − εS23) + c4(H24 − εS24) = 0

c1(H31 − εS31) + c2(H32 − εS32) + c3(H33 − εS33) + c4(H34 − εS34) = 0

c1(H41 − εS41) + c2(H42 − εS42) + c3(H43 − εS43) + c4(H44 − εS44) = 0

Integrals of the type Haa = α are called Coulomb integrals, integrals of the type Hab = β are
called resonance integrals, and integrals of the type Sab = δab are called overlap integrals.

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 Molecular Orbital Theory of Polyatomic Molecules
The secular determinant that is used to obtain the MO energies and the coef cients of the
AOs for 1,3-butadiene is:

(H11 − εS11) (H12 − εS12) (H13 − εS13) (H14 − εS14)

(H21 − εS21) (H22 − εS22) (H23 − εS23) (H24 − εS24)
=0
(H31 − εS31) (H12 − εS32) (H33 − εS33) (H34 − εS34)
(H41 − εS41) (H42 − εS42) (H43 − εS43) (H44 − εS44)

The rst is Sii = 1 and Sij = 0 unless i = j . It is also assumed that Hij = β if i and j are on
adjacent C atoms, Hij = α if i = j, and Hij = 0 otherwise.
Setting Hij = 0 for nonadjacent carbon atoms amounts to saying that the primary interaction
is between the neighboring 2pz orbitals. Hence, the secular determinant for butadiene is:

α−E β 0 0
β α−E β 0
=0
0 β α−E β
0 0 β α−E

By setting at the secular determinant all diagonal elements equal to α − E and off-diagonal
elements between neighbouring atoms equal to β, and all other elements are zero.

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 Molecular Orbital Theory of Polyatomic Molecules
The secular determinant can be expanded to yield the following equation, and then the
solutions for the π orbital energies
α−E β 0 0
β α−E β 0
=0
0 β α−E β
0 0 β α−E

On setting x = α − E and expanding the determinant, we obtain

x 4 − 3β 2 x 2 + β 4 = 0

This quartic in x is a quadratic equation in y = x 2, namely

y 2 − 3β 2 y + β 4 = 0

so its roots can be found by elementary methods:

1/2 1/2
3±5 3±5
( 2 ) ( 2 )
1/2 1/2
x= β and x=− β

We conclude that the energy levels are E = α ± 1.618β and E = α ± 0.618β

First, the coef cients of the AOs in the different MOs are not the same. Secondly, a pattern
of nodes is seen that is identical to the other quantum systems that have been solved.
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 Molecular Orbital Theory of Polyatomic Molecules
From the theory of determinants, an N × N tridiagonal determinant with equal elements
along the main diagonal and equal elements along a subdiagonal has the following roots:

(N + 1)
kπ
Ek = α + 2β cos ; k = 1,2,...,N

The coef cients of the orbitals can be found by substituting these energies into the secular
equations. For example, the four molecular orbitals of butadiene are found in this way to be

ψ1π = 0.372ϕA + 0.602ϕB + 0.602ϕC + 0.372ϕD E = α + 1.618β

ψ2π = − 0.602ϕA − 0.372ϕB + 0.372ϕC + 0.602ϕD E = α + 0.618β

ψ3π = − 0.602ϕA + 0.372ϕB + 0.372ϕC − 0.602ϕD E = α − 0.618β

ψ4π = 0.372ϕA − 0.602ϕB + 0.602ϕC − 0.372ϕD E = α − 1.618β

where ϕj is a 2pz -orbital on atom j . The composition of these molecular orbitals is

independent of the values of α and β (provided β ≠ 0).
Notice that the energy of the orbital increases with the number of nodes, and that the
amplitude of each coef cient follows a sine wave tted to the length of the molecule.
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 Molecular Orbital Theory of Polyatomic Molecules

Ligand Field Theory

Ligand eld theory is a kind of 3D version of Hückel theory, in which the composition of the
orbitals of a complex is largely determined by the symmetry of the environment.
The energies of the molecular orbitals, as well as structural, spectroscopic, magnetic, and
thermodynamic properties are parametrized in terms of the ligand eld splitting parameter, Δ.

• We denote the central metal ion by M and assume that it has the con guration d n.
• The ligands are denoted L, and
• We con ne attention to ML6 octahedral complexes with Oh symmetry.
• The orbitals of the ligands are denoted λ.

In particular, we suppose that each ligand i supplies an orbital λ (σ) that has local σ symmetry
with respect to the M − L bond.
Thus, in ligand eld theory, each Lewis-base ligand is simulated by a single orbital that
supplies two electrons.
It is also possible that possibility that the ligands can supply electrons from or accept
electrons into their π-orbitals, and denote the latter by λ (π).
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 Molecular Orbital Theory of Polyatomic Molecules

Ligand Field Theory: Spin Adapted Linear Combinations (SALCs)

The rst step in ligand eld theory is to set up symmetry-adapted linear combinations and
to identify the symmetry species of the d-orbitals on the central metal ion.
A glance at the Oh character table shows that in an octahedral environment, two of the d
-orbitals (dz2 and dx2−y2) span Eg and the remaining three (dxy, dxz, and dyz) span T2g.
Group theory show that the ligand σ -orbitals span A1g + Eg + T1u in Oh , and projection
operator techniques give the forms of the corresponding Spin Adapted Linear Combinations:

(6)
1/2
1
ψ(A1g) = (λ1(σ) + λ2(σ) + λ3(σ) + λ4(σ) + λ5(σ) + λ6(σ))

( 12 )
1/2
1 (σ)
ψ(Eg) = (a) (2λ5
+ 2λ6(σ) − λ1(σ) − λ2(σ) − λ3(σ) − λ4(σ)) and

1 (σ)
(b) (λ1 + λ2(σ) − λ3(σ) − λ4(σ))
2

(2)
1/2
1
ψ(T1u) = (a) (λ1(σ) − λ2(σ)) and

(2) (2)
1/2 1/2
1 (σ) 1
(b) (λ3
− λ4(σ)) and (c) (λ5(σ) − λ6(σ))

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 Molecular Orbital Theory of Polyatomic Molecules

Ligand Field Theory: Molecular Orbitals

Now we form MOs as linear combinations of the SALCs and the metal d-orbitals of the
same symmetry species, for only these combinations have non-zero net overlap.
It is apparent from ligand orbitals that dz2 has non-zero overlap with ψ(Eg, a) but not with
ψ(Eg, b); the opposite is true for dx2−y2. We therefore can expect an array of energy levels like

ψ(a1g) = ψ(A1g)
ψ(eg) = (a) c1 χ(dz2) + c2ψ(Eg, a) and (b) c′1 χ(dx2−y2) + c′2ψ(Eg, b)
ψ(t1u) = (a) ψ(T1u, a) and (b) ψ(T1u, b) and (b) ψ(T1u, c)
ψ(t2g) = (a) χ(dxy) and (b) χ(dyz) and (b) χ(dxz)

The molecular orbital energy level diagram for

an octahedral complex:
The bonding Eg combination is largely con ned to the ligands and
the antibonding combination is largely con ned to the metal ion.
The T2g orbitals are non-bonding atomic orbitals on the metal ion.
The A1g and T1u combinations labelled ‘bonding’ are con ned almost
entirely to the ligands and those labelled ‘antibonding’ are con ned
almost entirely to the metal.
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 Molecular Orbital Theory of Polyatomic Molecules

Ligand Field Theory: Ground State Con guration

1. There are 12 electrons to accommodate that are supplied by the ligands, and n electrons
supplied by the d n metal ion.
• 12e ll the two bonding Eg and four ‘bonding’ A1g and T1u orbitals: these electrons are largely
con ned to the ligands.
• Up to 6 of the remaining n electrons are free to occupy the three T2g orbitals on the metal
ion and the remainder will occupy the antibonding Eg combination, which is largely on the
metal ion too.

2. The ground-state electron con guration of the complex is the con guration that
corresponds to the lowest total energy.

3. The crucial quantity is the ligand eld splitting parameter, Δ , the energy separation
between Eg and T2g.
• If this splitting is large, then a d 4 complex, for instance, will adopt the con guration (T2g)4 with
one orbital doubly occupied.
• If the splitting is small, then it may be energetically advantageous for the complex to adopt the
con guration (T2g)3(Eg)1 with all four electrons in separate orbitals with parallel spins.
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 Molecular Orbital Theory of Polyatomic Molecules

Ligand Field Theory: Ground State Con guration

We should distinguish between the follow- ing two cases:
The strong- eld case, in which the ligand eld splitting parameter is large and it is
energetically favorable to occupy the T2g orbitals rst.
The weak- eld case, in which the ligand eld splitting parameter is small and it is
energetically favorable to occupy the Eg orbitals before the t orbitals are completely lled.
2g

The high- and low-spin arrangements that arise from weak and strong ligand elds
for complexes with four to seven d-electrons:
When the ligand eld splitting parameter is so large that a (T2g)4, (T2g)5, (T2g)6, or
(T2g)6(Eg)1 con guration is adopted, the spins need to pair. Such complexes are
classi ed as low-spin complexes.
When the ligand eld is weak, the complexes can be expected to be (T2g)3(Eg)1 ,
(T2g)3(Eg)2, (T2g)4(Eg)2 , and (T2g)5(Eg)2 . Such complexes are classi ed as high-spin
complexes.

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