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# Molecular Electronic Structure

The Born-Oppenheimer Approximation
Chem5350
Born and Oppenheimer pointed out that since nuclei are thousands of
M OLECULAR S TRUCTURE times more massive than electrons, they move much more slowly and
can be treated as being stationary in considering the motions of
electrons in molecules.
Professor Angelo R. Rossi Thus, a simpler electronic Schrödinger equation can be solved for each
fixed internuclear distance R.
http://homepages.uconn.edu/rossi The molecular vibrations can then be obtained by solving a Schrödinger
Department of Chemistry, Room CHMT215 equation for the motion of the nuclei in the average potential field
The Univerity of Connecticut produced by the electrons.

## Fall Semester 2013

angelo.rossi@uconn.edu

## The hydrogen molecule ion H2 + is the simplest molecule and will be

discussed in some detail as an introduction to the treatment of more
complicated molecules.

Ĥψ(rr 1 , R A , R B ) = Eψ(rr 1 , R A , R B )

r 1 is the vector locating the electron, and R A and R B are the vectors
locating the nuclei in a coordinate system.

## Coordinates for the hydrogen molecule ion H2 + . The protons are

labeled A and B

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The Hydrogen Molecule Ion H2 + The Hydrogen Molecule Ion H2 +

The Hamiltonian for the hydrogen molecule ion is given by The Schrödinger equation for the electronic motion is then

~ 2 ~2 e2 e2 e2 Ĥψe = Ee (R)ψe
Ĥ = − 2M (∇2A + ∇2B ) − ∇2
2me e
− 4πǫ0 r1A
− 4πǫ0 r1B
− 4πǫ0 R

where M is the mass of each nucleus, me is the mass of the electron, with the Hamiltonian for electronic motion given by
r1A is distance between the electron and nucleus A, and r1B is distance ~2 2 e2 e2 e2
between the electron and nucleus B, Ĥe = − ∇e − − −
2me 4πǫ0 r1A 4πǫ0 r1B 4πǫ0 R
The Born-Oppenheimer approximations is introduced to solve the
Schrödinger equation for the H2 + ion. containing the electronic kinetic energy, the electrostatic attractions of
the electrons to each nucleus, and the nuclear electrostatic repulsion.
The nuclear repulsion term is a constant since the internuclear distance
ψ(rr 1A , r 1B , R A , R B ) = ψe (rr A , r B , R ) × ψn (R
RA , R B ) R is fixed, and the electronic Schrödinger equation can be solved for all
R, giving the electronic energy Ee (R) as a function of R.

where ψn (R
R A , R B ) is the wave function for nuclear motion.

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## The Hydrogen Molecule Ion H2 + The Variational Method

The Born-Oppenheimer approximation shows that the nuclei move in The variational method provides an upper bound to the ground-state
the potential energy Ee (R) determined by the electronic motion, so the energy of a system.
Schrödinger equation for nuclear motion becomes
The ground-state wave function ψ0 and energy E0 satisfy the
 
~2 Schrödinger equation
− (∇2A + ∇2B ) + Ee (R) ψn (R
R A , R B ) = En ψn (R
RA , R B ) Ĥψ0 = E0 ψ0
2M
Multiply the above equation from the left by ψ0∗ and integrate over all
where En is the energy of nuclear motion which contains contributions
space to obtain
for translational, rotational, and vibrational motion. R ∗
ψ Ĥψ0 dτ
E0 = R 0 ∗
The wave function for nuclear motion ψn (R R A , R B ) is the product of the ψ0 ψ0 dτ
wave functions for translational, rotational, and vibrational motions. The denominator is not set equal to unity to allow for the possibility that
ψ0 is not normalized.

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The Variational Method The Variational Method

A theorem says that if we substitute another function φ for ψ0 and The variational principle states that an upper bound to E0 can be
calculate the corresponding energy according to calculated by using any trial function we wish.
R ∗
φ Ĥφdτ A trial function φ can be chosen such that it depends upon some
Eφ = R ∗ arbitrary parameters, α, β, γ, · · · , called variational parameters.
φ φdτ

then Eφ will be greater than the ground-state energy E0 The energy will also depend upon these variational parameters

This is the variational principle where Eφ ≥ E0 , and the equality holds Eφ (α, β, γ, · · · ) ≥ E0
only if φ = ψ0 , the exact wave function.
Now, Eφ can be minimized with respect to each of the variational
parameters to determine the best possible ground-state energy from
the trial wave function.

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The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

The approach used in solving the Schrödinger equation for the This type of function is referred to as a linear combination of atomic
hydrogen molecule ion is to use a trial wave function made up of orbitals or an LCAO molecular orbital. Since the two nuclei are
hydrogenlike atomic orbitals This approach is called molecular orbital identical, c1 = c2 = c.
theory.
For nuclei that are close, the 1s orbitals overlaps shown below:
Molecular properties calculated in this way are are approximate, but the
treatment can be improved to any desired accuracy.

## As trial wave functions for ψe (rr A , r B , R ) for the one-electron hydrogen

molecule ion, the following linear combination is used

ψ± = c1 1sA ± c2 1sB

where 1sA and 1sB are atomic hydrogen orbitals on protons A and B,
and c1 and c2 are constants.
The above diagram shows the magnitudes of the 1s wave functions on atoms A and B when they are 3a0
apart but not interacting. The abscissa is the distance from atom A along the internuclear axis in units of a0 .

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The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

In order to normalize the molecular orbital with the plus sign, the following integral The normalization can be written in terms of the overlap integral
must have the value of unity: Z  Z 

ψ+ ψ+ dτ = 1
c2 2 + 2 1sA 1sB dτ = c2 (2 + 2S) = 1
Substituting the wave function yields
Z so that
c2 (1s∗A + 1s∗B )(1sA + 1sB )dτ = 1 1
c= 1
Z Z Z Z [2(1 + S)] 2
c2 1s∗A 1sA dτ + c2 1s∗A 1sB dτ + c2 1s∗B 1sA dτ + c2 1s∗B 1sB dτ = 1 The normalized wave function with a plus sign is given by
• The first and last integrals are equal to 1 because the 1s orbitals are normalized. 1
• The second and third integrals are equal because the wave function is real and are ψg = 1 (1sA + 1sB )
called overlap integrals. [2(1 + S)] 2

## The normalized wave function with a negative sign is given by

1
ψu = 1 (1sA − 1sB )
[2(1 − S)] 2
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The Hydrogen Molecule Ion H2 + : Even and Odd Parity The Hydrogen Molecule Ion H2 + : Even and Odd Parity

When a molecule has a center of symmetry, the wave function may or The parity of an orbital is even (g) if
may not change sign when it is inverted through the center of symmetry. the wave function is unchanged un-
der inversion through the center of
• If ψ(x, y, z) = ψ(−x, −y, −z), the wave function is said to have even symmetry.
parity and is designated with a subscript g for gerade. The parity of an orbital is odd (u) if
the wave function changes sign un-
• If ψ(x, y, z) = −ψ(−x, −y, −z), the wave function is said to have odd der inversion through the center of
parity and is designated with a subscript u for ungerade. symmetry.
Homonuclear diatomic molecules
have a center of inversion while
heteronuclear diatomic molecules do
not.

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The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

## The overlap integral S can be evaluated analytically as a function of

internuclear distance R, and the result is given below
 
R2
S = e−R 1 + R +
3

## When R = 0, the two 1s orbitals overlap completely, and S = 1. As R is

increased to infinity, the overlap integral decreases asymptotically to
zero.

## (a) Magnitude of the normalized molecular orbital ψg when protons A

and B are separated by 3a0 . (b) Magnitude of the normalized molecular
orbital ψu . (c) Magnitude of ψg2 . (d) Magnitude of ψu2 .

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The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

Using the molecular orbitals (ψg or ψu ), the upper bound to the energy The integral HAA is called the Coulomb integral because the
of H2 + can be calculated using the variation principle: difference between HAA and the energy of a single hydrogen atom is
R ∗ R just that of the Coulomb interaction of nucleus B with an electron
R
ψ Ĥψdτ [c1 1sA + c2 1sB ]Ĥ[c1 1sA + c2 1sB ]dτ
R centered on nucleus A.
E= =
ψ ∗ ψdτ [c1 1sA + c2 1sB ]2 dτ Z  
e2 e2
HAA = E1s + − J, where J = 1sA 1sA dτ
c21 HAA + 2c1 c2 HAB + c22 HBB c21 HAA + 2c1 c2 HAB + c22 HBB 4πǫ0 R 4πǫ0 rB
E= =
c21 SAA + 2c1 c2 SAB + c22 SBB c21 + c1 c2 S + c22
R R J is called the electron repulsion integral
HAA = 1sA Ĥ1sA dτ = 1sB Ĥ1sB dτ = HBB  
R R 1
HABR = 1sA Ĥ1sBRdτ = 1sB Ĥ1sA dτ J = e−2R 1 +
SAA = 1sRA 1sA dτ = 1sRB 1sB dτ = SBB = 1 R
SAB = 1sA 1sB dτ = 1sB 1sA dτ = S

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The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

The integral HAB is referred to as the resonance integral. To find the minimum energy. the derivatives of E with respect to c1 and
  Z   c2 are set to zero.
e2 e2
HAB = SAB E1s + − K, where K = 1sB 1sA dτ To do this, the equation for the energy of H2 + is set rewritten in the form:
4πǫ0 R 4πǫ0 rB

K is called the exchange integral. E(c21 + 2c1 c2 S + c22 ) = c1 HAA + 2c1 c2 HAB + c22 HBB

## S Differentiating this equation with respect to c1 equals

K= − e−R (1 + R)
R
∂E 2
E(2c1 + 2c2 S) + (c + 2c1 c2 S + c22 ) = 2c1 HAA + 2c2 HAB
∂c1 1
and differentiating this equation with respect to c2 equals

∂E 2
E(2c1 S + 2c2 ) + (c + 2c1 c2 S + c22 ) = 2c1 HAB + 2c2 HBB
∂c2 1

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The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory The Hydrogen Molecule Ion H2 + : Molecular Orbital Theory

Since ∂c
∂E
and ∂c
∂E
are equal to zero for the minimum energy, the above The energy ∆Eg of the H2 + ion in the bonding orbital ψg relative to the
1 2
equations can be written as completely dissociated species H+ and H is given by

## c1 (HAA − E) + c2 (HAB − SE) = 0 J +K

∆g = Eg − E1s =
c1 (HAB − SE) + c2 (HBB − E) = 0 1+S

There is a nontrivial solution to these equations only if the determinant The energy ∆Eu of the H2 + ion in the antibonding orbital ψu relative to
of the coefficients is equal to zero the completely dissociated species H+ and H is given by
J −K
HAA − E HAB − SE ∆u = Eu − E1s =

HAB − SE HBB − E = 0 1−S

## This yields two solutions

J+K
Eg = E1s + 1+S
J−K
Eu = E1s + 1−S

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The Hydrogen Molecule Ion H2 + : Theory vs Experiment The Hydrogen Molecule Ion H2 + : Potential Energy Curves

Calculated Experimental
Equilibrium Separation (Re ) 2.50 a0 = 1.32 Å 1.06 Å
Binding Energy (kJ mol−1 ) 170 258

The simple molecular orbital wave function which was chosen does not
quantitatively explain the bonding in the hydrogen molecule ion, but this Calculated and experimental molec-
wave function can be improved by adding more terms. ular potential energy curves for H2 +
showing the variation of energy as
The next step is to add terms for the 2s and 2p orbitals on the two
the bond length is changed.
nuclei.
ψ = c(1sA + 1sB ) + c′ (2sA + 2sB ) + c′′ (2pzA + 2zB )

In the limit of adding more terms, the results obtained from the solution
of the Schródinger equation are in good agreement with experiment.

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The Hydrogen Molecule Ion H2 + : Orbital Interaction Diagram Molecular Orbital Description of the H2 Molecule

It is useful to represent the energies of molecular orbitals by use of an Using the Born-Oppenheimer approximation, the electronic Hamiltonian
orbital interaction diagram for the hydrogen molecule may written as
 
~2 e2 1 1 1 1 1 e2
Ĥ = − (∇21 + ∇22 ) + − − − − + +
2me 4πǫ0 rA1 rA2 rB1 rB2 r12 4πǫ0 R

## where the coordinates are defined in the figure below

• Since HAA and HBB are negative, and S is positive, Eg is more negative than Eu
and is the energy of the more stable molecular orbital.
• Since ψg is symmetrical around the internuclear axis, it is referred to as a σ, since
it is even, it is referred to as gerade, and since it is made up of two 1s orbitals, it is
designated as σg 1s.
• The less stable orbital is represented by the σu∗ 1s.

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Molecular Orbital Description of the H2 Molecule Molecular Orbital Description of the H2 Molecule

When the electronic Hamiltonian for the hydrogen molecule is used in Each electron can be assigned to an orbital, and the electronic wave
function for the molecule is the product of two wave functions for the two
Ĥψe = Ee (R)ψe electrons:
ψM O = ψi (1)ψj (2)
An exact solution cannot be obtained because of the 1
r12
term.
where i and j designate the different orbitals, and 1 and 2 designate the
This is the reason that the LCAO-MO method is used to obtain an
two electrons.
approximate solution.
According to the Pauli principle, two electrons with opposite spin can be
According to the LCAO-MO approach, molecular hydrogen is formed by
assigned to a given spatial orbital.
putting two electrons with opposite spin in the σg 1s orbital.
As a first approximation, we will assume that in the ground state of the
hydrogen molecule, the two electrons are placed in a σg orbital.

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## Molecular Orbital Description of the H2 Molecule The H2 Molecule: Theory vs Experiment

The electronic configuration of H2 will be described as (1σg )2 . The approximate energy of the hydrogen molecule is obtained by
The wave function for electron 1 in the 1σg molecular orbital is calculating the expectation of the Hamiltonian using this wave function
represented by Z
∗ 2 2
E = ψM O [(1σg ) ]Ĥel ψM O [(1σg ) ]dτ
1
1σg (1) = 1 [1sA (1) + 1sB (1)]
[2(1 + S)] 2
Calculated Experimental
The wave function satisfying the antisymmetric requirement is given by Equilibrium Separation (Re ) 0.84 Å 0.741 Å
a Slater determinant, and so the approximate wave function for the Dissociation Energy (kJ mol−1 ) 255 458
ground state of the hydrogen molecule is given by the following Slater
determinant: Although simple MO theory does account for a large proportion of the
binding energy of the H2 molecule, it has to be extended to yield
1 1σ (1)α(1) 1σg (1)β(1) accurate results.
ψM O [(1σg )2 ] = √ g
2 1σg (2)α(2) 1σg (2)β(2)

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Deficiency in the Approximate MO Wave function Deficiency in the Approximate MO Wave function

One can see the deficiency in the approximate wave function by Schematic E(R) curves for the LCAO-MO (red
curve) and exact (blue curve) for H2 .
multiplying out the spatial part:
Note that the LCAO-MO curve dissociates to a
mixture of neutral and ionic species.
1s (1)1s (2) + 1s (1)1sB (2) + 1sB (1)1sA (2) + 1sB (1)1sB (2)
| A {z A } | A {z } | {z } The MO curve shows that the model does not
correctly describe H2 in the limit of large R.
ionic covalent ionic
The horizontal dashed line is the zero of en-
• The first and last term correspond to forms of the hydrogen ergy corresponding to two H atoms at infinite
separation.
molecule with ionic bonding: H− + + −
A HB and HA HB . The improved results are given in the table be-
• Thus, at R = ∞, the molecular orbital wave function describes a low:
state which is 50 % H+ + H− and 50 % H · +H· which is clearly not
correct. Equilibrium Separation (Re ) 0.749 Å 0.741 Å
• This problem can be reduced by introducing variable coefficients c1 Dissociation Energy (kJ mol−1 ) 386 458
and c2 in
The inclusion of one variational parameter
ψ = c1 (R)ψcovalent + c2 (R)ψionic leads to significant improvement.

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Molecular Orbitals for Many-Electron Atoms Molecular Orbitals for Many-Electron Atoms

In MO theory, an electron is associated with a wave function that is Each of the entries in the Slater determinant is an MO that is expressed
delocalized over the entire molecule. as a linear combination of AOs denoted by φi :
The MOs (σi ) are constructed from linear combinations of atomic X
orbitals (AOs) leading to the term LCAO-MO Model. σi (1) = cij φj (1)
j
The many-electron molecule must satisfy the Pauli exclusion principle
leading to the expression of a wave function of an n-electron molecule The sum extends over AOs on all the atoms in a molecule, and the
as a Slater determinant number in parentheses refers to the electron under consideration.
For example, in H2 , both electrons are in the σ1 molecular orbital
σ1 (1)α(1) σ1 (1)β(1) . . . σm (1)β(1)

1 σ1 (2)α(2) σ1 (2)β(2) . . . σm (2)β(2)
ψ(1, 2, 3, . . . , n) = √ σ1 (1) = (φ1,1sA + φ1,1sB )
n! . . . ... ... ...

σ1 (n)α(n) σ1 (2)β(2) . . . σm (n)β(n)

where m = n
2
if n is even, and m = n+1
2
if n is odd.

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How Are Observables for Molecules Calculated? Computing Molecular Orbital Energies

Observables for a diatomic molecule such as the dipole moment, the Although the optimization of the cij is best carried out by a computer, we can carry out
bond dissociation energy, the bond length, and the ionization energy are a simple calculation by having one atomic orbital on each atom:
ultimately all related to the MOs and to the expansion coefficients cij . σ1 = c11 φ1 + c12 φ2
Therefore, we need a method to determine the cij in a given MO. where φ1 and φ2 are AOs on the different atoms.
• Assume that the atomic orbitals have been chosen. To determine the optimal values for these coefficients, the MO energy is minimized
• The variational method is used to determine the optimal values for with respect to the values of the AO coefficients.
cij . The expectation value of the energy is given by
R ∗
<ǫ> = Rσ1 ∗Ĥσ1 dτ
σ1 σ1 dτ
R
= R [c11 φ1 +c12 φ2 ]Ĥ[c11 φ1 +c12 φ2 ]dτ
(c11 φ1 +c12 φ2 )∗ (c11 φ1 +c12 φ2 )dτ
R R R
(c11 )2 φR1∗ Ĥφ1 dτ +(c21 )2 Rφ2∗ Ĥφ2 dτ +2c11 c21R φ∗1 Ĥφ2 dτ
= (c11 )2 φ∗ 2 φ∗ φ∗
1 φ1 dτ +(c12 ) 2 φ2 dτ +2c11 c12 1 φ2 dτ

## (c11 )2 H11 +(c12 )2 H22 +2c11 c21 H12

<ǫ> = (c11 )2 +(c12 )2 +2c11 c12 S12

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Solving for Molecular Orbital Energies and Coefficients MO ǫi and cij for Homonuclear Diatomic Molecules

To find the minimum energy, the derivatives of ǫ with respect to c11 and c21 are set to For a homonumclear diatomic molecule such as H2 , Be2 , · · · , F2 , H11 = H22
zero. leading to the following two solutions
Differentiating this equation with respect to c11 and c12 equals H11 +H12
ǫ1 = 1+S12
∂ǫ ǫ2 = H11 −H12
(2c11 + 2c12 S12 )ǫ + ((c11 )2 + (c12 )2 + 2c11 c12 S12 ) = 2c11 H11 + 2c12 H12 1−S12
∂c11
ǫ1 and ǫ2 correspond to the bonding and antibonding MO energies, respectively.
∂ǫ
(2c12 + 2c11 S12 )ǫ + ((c11 )2 + (c12 )2 + 2c11 c12 S21 ) = 2c12 H22 + 2c11 H12 The ǫi can be obtained from the following formulas:
∂c12
Since ∂ǫ
∂c11and ∂ǫ
∂c21 are equal to zero for the minimum energy, the above equations • Assume H11 and H22 can be approximated by the ionization energy of the neutral
can be written as atom. √
• H12 can be calculated using the approximation: H12 = −1.75S12 H11 H22
c11 (H11 − ǫ) + c12 (H12 − ǫS12 ) =0
c11 (H12 − ǫS12 ) + c12 (H22 − ǫ) =0 The coefficients cij can then be obtained from the following equations:
There is a nontrivial solution to these equations only if the determinant of the
c11 (H11 − ǫ) + c12 (H12 − ǫS12 ) =0
coefficients is equal to zero
c11 (H12 − ǫS12 ) + c12 (H22 − ǫ) =0

H11 − ǫ H12 − ǫS12

H12 − ǫS12 H22 − ǫ =0

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The H2 + and H2 Molecules Heteronuclear Diatomic Molecule: HF

For both the H2 + and H2 molecules, H11 = In this case H11 6= H22 .
H22 = -13.6 eV, the ionization energy of H. Let φ1 be a hydrogen 1s orbital with
A reasonable value is assumed for the over- H11 = -13.6 eV, and let φ2 be a fluo-
lap: S = 0.30. Using these values yields rine 2pz orbital with H22 = -18.6 eV.
ǫ1 = -16.0 eV and ǫ2 = -9.2 eV. The two MOs have the form
• The energy of the bonding orbital is low- σ1 = C11 φH1s + c12 φF 2pz
ered relative to H11 by 2.4 eV. σ2 = C21 φH1s + c22 φF 2pz
• The energy of the antibonding orbital is
raised relative to H11 by 4.4 eV. Given an overlap S = 0.30, H12 =
-8.35 eV.
The MO energy results for H2 can be con-
Solving the equation for the energies
veniently summarized in a molecular orbital
gives ǫ1 = -19.6 eV (the bonding
energy diagram.
MO), and ǫ2 = -10.3 eV (the anti-
bonding MO).

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The HF Molecule: Obtaining Coefficients for the MOs Obtaining MO Coefficients for the HF Molecule

## For ǫ1 = -19.6 eV For ǫ2 = -10.3 eV

c11 (H11 − ǫ1 ) + c12 (H12 − ǫ1 S12 ) = 0 c21 (H11 − ǫ1 ) + c22 (H12 − ǫ1 S12 ) = 0
Substitution of the appropriate values gives Substitution of the appropriate values gives

c11 (-13.6 + 19.6) + c12 (-8.35 + 0.30 x 19.6) = 0 c21 (-13.6 + 10.3) + c22 (-8.35 + 0.30 x 10.3) = 0

c11 c21
= 0.41 = -1.58
c12 c22
Using this result in the normalization equation Using this result in the normalization equation

c211 + c212 + 2c11 c12 S12 = 1 c221 + c222 + 2c21 c22 S12 = 1

yields c11 = 0.34, c12 = 0.84 and σ1 = 0.34φH1s + 0.84φF 2pz . yields c21 = 0.99, c22 = -0.63 and σ2 = 0.99φH1s − 0.64φF 2pz .

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Obtaining MO Coefficients for the HF Molecule The Molecular Orbital Energy Diagram

The relative magnitude of the coefficients of the AOs gives information about the By convention, the AOs for the atoms are shown on
charge distribution in the molecule. the left and right side of the diagram.
The MOs are generated by combining the AOs are
Consider an electron in the bonding MO of HF given by σ1 = 0.34φH1s + 0.84φF 2pz . shown in the middle.
The probability density of this orbital can be calculated as
The molecular energy diagram allows us to deter-
Z Z mine the energies of the MOs relative to the AOs.
|ψ 2 |dτ = σ1∗ σ1 dτ = c211 + c212 + 2c11 c12 S12 = 1 The bonding MO is lower in energy than the lower
of the two AOs, and the antibonding MO is higher in
energy than the higher of the two AOs.
This gives
Empirical rules can be used to obtain a reasonable
• c211 + c11 c12 S12 = 0.21 is the probability of finding the e− around the H atom. size basis set to describe the electronic structure of
first and second row diatomic molecules at a quan-
• c212 + c11 c12 S12 = 0.79 is the probability of finding the e− around the F atom. titative level.
• 2c11 c12 S12 = 0.17 is the probability that is shared between the H and F atoms.
For H and He, only 1s orbitals are used; for Li → Ne,
the 2s, 2px , 2py , and 2pz atomic orbitals included

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## Effect of Symmetry on Overlap Overlap as a Function of R

Only orbitals of the same symmetry will combine with one another.
The adjacent figure indicates how over-
Nonzero overlap between two AOs occurs lap varies with distance for different or-
• if both AOs are cylindrically symmetric with respect to the molecular bitals.
axis (σ MOs) or As discussed earlier, a nonzero overlap
• if both AOs have a common nodal plane that coincides with the of atomic orbitals is necessary for chemi-
molecular axis (π orbitals). cal bond formation.

## The overlap of two s or two px and py or-

bitals is maximized when R = 0, but the
overlap of an s orbital with a pz orbital has
it maximum value at a larger internuclear
distance.

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Symmetry Operations for Diatomic Molecules Molecular Orbitals for Homonuclear Diatomic Molecules

All MOs of diatomic molecules can be divided into two groups with regard to rotation
• If this rotation leaves the MO unchanged, the MO has σ symmetry. Combining s
orbitals always gives rise to σ MOs for diatomic molecules.
• If the molecule has one nodal plane containing the molecular axis, the MO has π
symmetry. Combining πx or πy AOs always gives rise to π MOs.
The second operation of inversion through the center of the molecule is valid only
for homonuclear diatomic molecules.
• If this operation leaves the molecule unchanged, the MO has g symmetry:
σ(x, y, z) → σ(−x, −y, −z).
• If σ(x, y, z) → −σ(−x, −y, −z), the MO has u symmetry.

## Contour plots of several bonding and antibonding orbitals. The yellow

arrows show the transformation σ(x, y, z) → σ(−x, −y, −z).
If the amplitude changes sign under this transformation, it has u
symmetry. If it is unchanged, it has g symmetry.
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Symmetry Labels for Homonuclear Diatomic Molecules σ and π Orbitals for Diatomic Molecules

## Two different notations are commonly used to describe MOs in

homonuclear diatomic molecules. Two types of MOs can be generated from
2p AOs.
1. The MOs are classified according to increasing energy.
For example, a 2σg orbital has the same symmetry, but a higher 1. If the axis of the 2p orbital lies on
energy than the 1σg orbital. the intermolecular axis (by conven-
tion the z-axis), a σ MO is generated.
2. The MOs are classified by the AOs from which they were This specific MO is called 3σg or
σg (2pz ).
generated.
Thus, the σg (2s) MO has a higher energy than the σg (1s) MO. 2. Combining 2px or 2py orbitals on
each atom gives a π MO because the
A superscript ∗ is used to designate antibonding MOs for both MO has a nodal plane containing the
molecular axis.
classifications.
These MOs are degenerate in
energy and are called 1πu or
πu (2px ), πu (2py ) MOs.

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Mixing Atomic Orbitals to Form Molecular Orbitals Labeling Molecular Orbitals of Diatomic Molecules

In principle, it is possible to take a linear combination of all the basis The MOs that used to describe chemical bonding in first and second
functions of the same symmetry (either σ or π) when constructing MOs. row homonuclear diatomic molecules is shown in the table below.
However, an additional criterion based on orbital energies, reduces the The AO that is the major contributor to the MO is shown in the last
number of AOs which mix into a given MO. column, and the minor contribution is shown in parenthesis.

• For example, the mixing between 1s and 2s AOs for second row
diatomics can be neglected at our level of discussion.
• However, for these same molecules, the 2s and 2pz AOs both have σ
symmetry and will mix if their energies are not significantly different.

## Since the energy difference between 2s and 2pz orbitals increases in

going from Li → F, the s-p mixing decreases for second-row diatomics
in the order Li2 , B2 , . . . , O2 , F2 .

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## Energy Ordering of Molecular Orbitals Orbital Interaction Diagrams for H2 + and H2

It is useful to think of MO formation as a two step process: The interaction of 1s orbitals on each
atom gives rise to a bonding and anti-
1. create separate MOs from the 2s and 2p AOs. bonding MO as shown schematically in
2. combine the MOs of the same symmetry to create the final MOs
that include s − p mixing. Each MO can hold two electrons of oppo-
site spin.
For the sequence H2 → N2 , the orbital energies increase in the The configurations of H2 and He2 are
sequence (1σg )2 and (1σg )2 (1σu∗ )2 , respectively.
For H2 both electrons are in the 1σg or-
1σg < 1σu∗ < 2σg < 2σu∗ < 1πu < 3σg < 1πg∗ < 3σu∗ bital which is lower than the 1s AOs.
In the MO model for He2 , there are two
Moving across the periodic table to O2 and F2 , the order of the 1πu and electrons each in the 1σg and 1σu∗ or-
the 3σg changes. bitals. Because the 1σu∗ is greater than
zero, He2 is not a stable molecule in this
1σg < 1σu∗ < 2σg < 2σu∗ < 3σg < 1πu < 1πg∗ < 3σu∗ model.

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Schematic MO Energy Diagram for the Valence Electrons in F2 Schematic MO Energy Diagram for the Valence Electrons in N2

F2 has s and p valence electrons, but the N2 also has s and p valence electrons, but unlike
s − p mixing can be neglected because F2 , the s − p mixing is not negligible because the 2s
AO lies below the 2p AO by only 12.4 eV.
the 2s AO lies 21.6 eV below the 2p AO.
Therefore, the 2σ and 3σ MOs have significant con-
The configuration for F2 is tributions from both the 2s and 2pz AOs.
The configuration for N2 is
(1σg )2 (1σu )2 (2σg )2 (2σu∗ )2 (3σg )2 (1πux )2 (1πuy )2 (1πgx
∗ 2 ∗ 2
) (1πgy )
∗ 2
(1σg )2 (1σu )2 (2σg )2 (2σu ) (1πux )2 (1πuy )2 (3σg )2
For this molecule, the 2σ MO is essen-
tially described by a single 2s AO on Note that the mixing has changed the shape of the
2σ and 3σ MOs of N2 .
each atom while the 3σ MO is described
The 2σu ∗ has become less antibonding, and the 3σ
quite well by a single 2pz AO on each MO has become less bonding for N2 in comparison
g

## atom. The degenerate p and π are shown with F2 .

slightly offset in energy. The degenerate p and π are shown slightly offset in
energy.
The dominant contributions in energy are
The dominant contributions in energy are shown in
shown in solid lines, and minor contribu- solid lines, and minor contributions of s − p mixing
tions of s − p mixing are neglected. are neglected.
From the overlaps of the MOs, the triple bond in N2
arises from the occupation of the 3σg , 1πux , and
1πuy MOs.

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MO Energy Levels for Second-Row Homonuclear Diatomics Bond Order, Bond Energy, and Bond Length

The MOs are filled in sequence of increasing en- The concept of bond order can be defined as
ergy, and the number of unpaired electrons for a
diatomic molecule can be predicted.
total bonding electrons−total antibonding electrons
The energy of the MOs tends to decrease with in- bond order = 2
creasing atomic number which is a result of larger
effective charge and smaller atomic size lower-
ing the corresponding AO energies. The bond energy is expected to be very small for a bond order of zero.
The 3σg orbital energy falls more rapidly than the The trend in bond energies and force constants shows the same trend as the bond
1πu orbital because the s − p energy splitting in-
orders.
creases in going from Li2 to F2 .
The mixing which occurs between the 2pz orbitals For a given atomic radius the bond length is expected to vary inversely with bond
composing the 3σg orbital and the 2s orbitals of the order.
2σg decreases.
Because the 2px and 2py AOs don’t mix with the 2s • The trend is approximately followed for the series Be2 → N2 .
AO, the 1πu remains constant across this series of
atoms resulting in a switch in the energy ordering of • The trend is not followed for H2 → Li2 because the atomic orbital changes from 1s
the 3σg and 1πu MOs for O2 and F2 . to 2s and because the He2 molecule is not really bonded.
Both B2 and O2 are predicted to have two unpaired
electrons and, thus, to have a net magnetic moment
(paramagnetic molecule) which is in good agree-
ment with experiment.

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Bond Order, Bond Energy, and Bond Length Heteronuclear Diatomic Molecules

## New issues arise when chemical bond formation in heteronuclear

By looking at the trend in bond orders,
MO theory can provide an understand-
diatomic molecules is considered.
ing of the trends in the binding en-
ergies, bond lengths, and vibrational 1. When two interacting AOs of different energies interact, the
force constants for diatomic molecules. coefficients of the AOs in the MOs have different magnitudes.
As the number of electrons increases,
• The coefficient of the lower energy AO is greater than that of
the bond energy has a pronounced max-
imum for N2 and a smaller maximum for the higher AO in the bonding MO.
H2 . • The opposite is true for the antibonding MO.
The bond length also increases in the se- 2. The g and u symmetries do not apply and the MOs are numbered
ries H2 → F2 , but exhibits a more compli- differently:
cated trend for smaller molecules.
The vibrational force constant k shows Homonuclear 1σg 1σu∗ 2σg 2σu∗ 1πu 3σg 1πg∗ 3σu∗ . . .
the same trend as the bond energy Heteronuclear 1σ 2σ 3σ 4σ 1π 5σ 2π 6σ . . .
above.

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The Molecular Orbital Energy Diagram for HF Hückel MO Theory for Conjugated Molecules

## Consider planar, conjugated hydrocarbons:

• acyclic polyene: Cn Hn+2
• monocyclic polyene: Cn Hn
The 2s electrons are almost completely • polycyclic polyenes: Cn Hn−2 , Cn Hn−4 , . . .
localized on the F atom.
The 1π electrons are completely local- Electronic Configurations of Carbon and Hydrogen
ized on the F atom because the 2px and 6 C: 1s2 2s2 2p2 - the C atom contributes four valence electrons.
2py orbitals have a zero overlap with the
1 H: 1s - the H atom contributes one valence electron.
Schematic energy diagram showing 1
the AO and MO orbital energy 1s orbitals of H.
levels for the valence electrons in
The admixture of s and p in the 4σ and
Octet Rule
HF.
5σ ∗ MOs changes the electron distribu- Atoms other than H tend to be surrounded by 8 electrons either through
The 3σ, 4σ, and 1π MOs for HF can tion somewhat when compared with a bonding or sharing.
be described as follows: homonuclear diatomic molecule.

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Hückel MO Theory for Conjugated Molecules Hückel MO Theory for Planar Conjugated Molecules

Lewis Structure of C2 H4 We are primarily interested in obtaining the electronic energies and wave functions for
planar unsaturated molecules like benzene.
C2 H4 - total valence electrons = 4 × 1 + 2 × 4 = 12
ĤΨ = EΨ

In planar unsaturated molecules, the π MOs will not mix with the σ MOs because of

## differences in their symmetry

Ψ = ψσ × ψπ
We will be mainly concerned with the pz orbitals, since they are the Ĥ = Ĥσ + Ĥπ + Ĥσ π
predominant influence on reactivity.
We assume that we know ψσ and can then treat the σ system as merely providing part
The underlying σ electrons provide an effective potential for the π of the effective potential in which the π electrons move.
electrons.
Hπef f (σ)ψπ = Eπ ψπ where Ĥπef f (σ) = Ĥπ + Eσ

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Hückel MO Theory for Ethylene Variational Principle for Hückel Model Applied to Ethylene

R
In general, for n carbon atoms, there are n basis functions or n × pz ψj Ĥπef f ψj dτ
orbitals: ǫj = R
Xn ψj ψj dτ
ψj = crj φr
(c11 φ1 + c21 φ2 )Ĥπef f (c11 φ1 + c21 φ2 )dτ
r=1 ǫj = R
(c11 φ1 + c21 φ2 )(c11 φ1 + c21 φ2 )dτ
where ψj is MO j.
Thus, The following definitions are given
Hπ ψj MO = ǫj ψj MO R R
H11 = R φ1 Ĥπef f φ1 dτ H12 = R φ1 Ĥπef f φ2 dτ
As an example, the ethylene wave functions (ψπ , ψπ∗ ) are taken as S11 = φ1 φ1 dτ S12 = φ1 φ2 dτ
linear combinations of pz orbitals on each carbon center (LCAO-MO).
∂ǫj
∂c11
= 0 : c11 (H11 − ǫj S11 ) + c21 (H12 − ǫj S12 ) = 0
ψ1 (ψπ ) = c11 φ2pz1 + c21 φ2pz2 ψ2 (ψπ∗ ) = c21 φ2pz1 + c22 φ2pz2 ∂ǫj
∂c21
= 0 : c21 (H11 − ǫj S12 ) + c22 (H22 − ǫj S22 ) = 0
where φ2pz1 and φ2pz2 are pz orbitals on C1 and C2 , respectively.   
H11 − ǫj S11 H12 − ǫj S12 c11
=0
H21 − ǫj S12 H22 − ǫj S22 c21

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The Hückel Approximation The Hückel Approximation for Ethylene

## R The secular determinant for ethylene becomes

Hrr = φr Ĥφr dτ = α Coulomb Integral
α−ǫ β
( =0
R β α−ǫ
β, r bonded to s
Hrs = φr Ĥφs dτ = Resonance Integral
0, otherwise
Solution of this determinant leads to the following results:
(
R 1, if r = s • The energies of the two MOs are ǫ = α ± β.
Srs = φr φs dτ = Overlap Integral √
0, if r 6= s
• c11 = c21 = 1/ 2 for ǫ = α + β

According to the Hückel approximation, the previous set of linear • c11 = −c21 = 1/ 2 for ǫ = α − β
equations for ethylene become:
The parameter α plays the role of reference energy because it is the
   energy of a 2pz AO in the absence of delocalization.
α − ǫj β c11
=0
β α − ǫj c21

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The Hückel Approximation for Ethylene The Hückel Model for the Allyl System

α−ǫ β 0

β α−ǫ β =0

0 β α−ǫ

α−ǫ
β 1 0

1 α−ǫ
1 = 0
β
0 1 α−ǫ
β

## Energy levels and molecular orbitals for the π electrons in ethylene.

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The Hückel Model for the Allyl System The Hückel Model for the Allyl System

Define
ǫ−α Eigenvalues
−x =
β

−x 1 0
ǫ1 = α − 2β
1 −x 1 = 0

0 1 −x ǫ2 = α
The solution of the above determinant leads to the following values for x √
ǫ3 = α + 2β

x3 − 2x = 0 x = ± 2, 0

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The Hückel Model for the Allyl System The Hückel Model for the Allyl System

Eigenvectors Eigenvectors
The following is obtained from the secular equations:
1 2
c11 = c31 = ; c21 = √
− c11 x3 + c21 = 0 2 2
c11 − c21 x3 + c31 = 0

c21 x3 − c31 x3 = 0

## c211 + c221 + c231 = 1

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Generalization of Hückel Model to A Planar Molecule Generalization of Hückel Model to A Planar Molecule
with n Basis Functions with n Basis Functions
  
H11 − ǫj S11 H12 − ǫj S12 . . . H1n − ǫj S1n c11 R
 H21 − ǫj S12 H22 − ǫj S22 . . . H2n − ǫj S2n  
  c21 
 Hrr = φr Ĥφr dτ = α Coulomb Integral
 .. ..  .. =0 (
 . .  .  R β, r bonded to s
Hn1 − ǫj Sn2 Hn2 − ǫj Sn2 . . . Hnn − ǫj Snn cn1 Hrs = φr Ĥφs dτ = Resonance Integral
0, otherwise

HC j = ǫj SC j (
R 1, if r = s
Srs = φr φs dτ = Overlap Integral
     
0, if r 6= s
H11 ... H1n S11 ... S1n ǫ1 ... 0
 . .   . .   . .. . 
H= . .  S= . .  E= . . . 
. . . . . .
Hn1 ... Hnn Sn1 ... Snn 0 ... ǫn The overlap matrix is now a unit matrix:
HC = ESC !
1 ... 0
. .. .
S= .
. . .
.
0 ... 1

HC = EC
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Generalization of Hückel Model to A Planar Molecule The Hückel Model for the 1,3-Butadiene
with n Basis Functions

## in the Hückel approximation

 
The exists a unitary transformation U such that 0 1 0 0
 1 0 1 0 
H=
 0

U† = U−1 , UU−1 = 1 1 0 1 
0 0 1 0
Then
−1
UHU UC = E |{z}
| {z } |{z} UC
D C′ C′ Perform diagonalization using mathematical software.
′ ′
DC = EC
   
λ1 ... 0 ǫ′1 ... 0
 . . .   . .. . 
D =  .. .. ..  = E =  .. . ..  λn = ǫ′n = − α−ǫ
β
n

## 0 ... λn 0 ... ǫ′n

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The Hückel Model for the 1,3-Butadiene The Hückel Model for the 1,3-Butadiene

occupied
X
Eπ = ν j ǫj
j=1

## α and β are negative quantities.

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Charge and Bond Order Matrix Aromaticity of Benzene: Valence Bond Theory

Charge In terms of valence bond theory the benzene molecule is described as a resonance
hybrid of two canonical Lewis structures containing three isolated C=C double bonds.
The π electron density on atom r is given as
Both of these canonical resonance structures are shown below in the figure below:
occupied n
X X
qr = prr = νj c2rj qr = N (Total Number of π Electrons) H
j=1 r=1 H❜
❜✧✧ ✧H
✧❜❜✧ ✧✧❜❜
✧ ✧✧❜
❜❜
✧ ✧ ❜
where νj is the number of electrons (0, 1, 2) in MO j.
✧❜❜
❜ ✧❜ ❜
❜ ✧
Bond Order H ✧ ❜✧ ❜ H ❜✧✧
❜ ❜❜✧
✧✧

## The bond order between two atoms r and s is given as H

ΨI ΨII
occupied
X
prs = νj crj csj For Valence Bond theory, delocaalization energy points to an ambiguity because the
j=1 total wave function is constructed from localized wave functions:

## where νj is the number of electrons (0, 1, 2) in MO j. ΨTot = AΨI + BΨII

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Aromaticity of Benzene: Molecular Orbital Theory Delocalized Molecular Orbitals of Benzene and π-Energies

## The molecular orbital description of benzene provides a delocalized picture in which

the electron density is smeared out in a π cloud above and below the ring.
This can be emphasized by placing a circle inside the benzene ring

✗✔
✧✧❜❜

✖✕
ΨTotal
❜❜✧✧

The molecular orbitals are considered to delocalized over the entire molecule, and this
extra stability of planar aromatic conjugated hydrocarbons which is called the
resonance delocalization energy can be calculated using Hückel theory.
From experiment it is known that benzene does not have three isolated C-C double
bonds but consists instead of a delocalized π electron system which produces an
extra stability called resonance stabilization energy or aromaticity.

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## Delocalization Energy Hückel (4n + 2 ) Rule

In general, the heat of hydrogenation of an isolated double bond (essentially an Monocyclic planar systems of trigonally hybridized atoms that contain
ethylene double bond) in butene is about 30.3 kcal/mol. (4n + 2) p-electrons (where n is a non-negative integer) will exhibit
Adding the heat of hydrogenation of localized double bonds appears to be violated aromatic character.
when the double bonds are conjugated.
The rule is generally limited to n = 0 - 5.
• Thus, the heat of hydrogenation for trans-1,3-butadiene is 57.1 kcal/mol compared
with the 60.6 kcal/mol for a pair of ethylene double bonds. This rule is derived from the Hückel MO calculation on planar
• Since the hydrogenation in each case is butane, the energy difference of 3.5
kcal/mol must be due to the greater stability of conjugated double bonds.
monocyclic conjugated hydrocarbons (CH)m where m is an integer
equal to or greater than 3 according to which (4n + 2) p-electrons are
There is a theoretical parallel to the additivity of localized π double bonds versus contained in a closed-shell system.
delocalized π bonds.
The Hückel Molecular Orbital (HMO) energy for butadiene is 4 α + 4.472 β. Systems containing 4n p-electrons such as cyclobutadiene and the
For a pair of isolated double bonds, the Hückel energy of ethylene is doubled to
cyclopentadienyl cation are antiaromatic and are not considered as
obtain 4 α + 4 β. stable.
The HMO method indicates that the double bonds of the butadiene molecule are
stabilized by 0.472 β called the delocalization energy.

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Hückel (4n + 2 ) Rule Delocalization Energies of Several Cyclic Polyenes

## Examples of systems that obey the Hückel rule include:

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