36 Homonuclear Diatomic Molecules

Other homonuclear diatomic molecules (e.g., Li

2
, O
2
, He
2
, F
2
, N
2
, ...) can be described ac-
cording to the LCAO approach introduced with the study of the H
+
2
molecule. A general feature
of the LCAO method is that a combination of two atomic orbitals on different centers gives two
molecular orbitals (MO). One of these molecular orbitals is called bonding and the other one is
called antibonding. The bonding state is more stable than the system of innitely separated atomic
orbitals. On the other hand, the antibonding state is less stable than the isolated atomic orbitals. The
description of the H
+
2
molecule discussed in previous sections can be summarized by the following
diagram:

_
1S
A
1S
B

@
@
@
@
@R

_
+

_
+ +
-
-

u
1S

g
1S
This diagram introduces the nomenclature of states of homonuclear diatomic molecules, which is
determined by the following aspects:
1. Nature of the atomic orbitals in the linear combination (e.g., 1S orbitals in the study of the
H
+
2
molecules).
2. Eigenvalue of

L
z
, with z the internuclear axis (e.g., such eigenvalue is zero for the H
+
2
molecule and, therefore, the orbital is called ).
3. Eigenvalue of the inversion operator through the center of the molecule (e.g., g when the
eigenvalue is 1, and u when the eigenvalue is -1).
4. Stability with respect to the isolated atoms (e.g., an asterisk indicates that the state is unstable
relative to the isolated atoms).
Other homonuclear diatomic molecules involve linear combinations of p orbitals. Such linear
combinations give rise to type orbitals when there is no component of the angular momentum
in the bond axis (e.g., we choose the bond axis to be the z axis). An example of such linear
combination is represented by the following diagram:
86
`
_
`
_
`
_
`
_
+ +
2P
0
(A) 2P
0
(B)

@
@
@
@
@R

u
2P

g
2P
`
_
`
_
+
`
_
+
In order to classify molecular states according to eigenvalues of

L
z
, we make linear combinations
of eigenfunctions of

L
z
with common eigenvalues. There are four possible states:
m= 1: 2P
+1
(A) 2P
+1
(B),

..

u
2P
+1
,

..

g
2P
+1
,
m=-1: 2P
1
(A) 2P
1
(B),
u
2P
1
,

g
2P
1
.
All of these linear combinations are states, because = |m| = 1 for all of them. In order to
justify their symmetry properties with respect to inversion we analyze the following particular case,

u
2P
+1
= 2P
+1
(A) + 2P
+1
(B) =
1
8

(
z
a
)
5/2
(e
i
A
e

zr
A
2a
r
A
sin
A
+ e
i
B
e

zr
B
2a
r
B
sin
B
),
which is represented by the following diagram:
87
-

u
2P
+1
orbital
A
(x, y, z)
r
A

r
A

B
B
r

B
r
B
g g
,
,
(x, y, z)
z nodal line
This diagram shows that under inversion through the origin, coordinates are transformed as follows,
r
A
r
B
,
A

B
,
r
B
r
A
,
B

A
,

A
=
B
= ,
+ ,
e
i(+)
= e
i
e
i
= e
i
, because e
i
= Cos
. .
1
+i Sin
..
0
.
The states constructed with orbitals P
1
differ, relative to those constructed with orbitals p
+1
, only
in the sign of phase introduced by the following expression,

g
2P
+1
=
1
8

(
z
a
)
5/2
e
i
(e

zr
A
2a
r
A
sin
A
+ e

zr
B
2a
r
B
sin
B
).
This function has a nodal xy plane and is described by the following diagram:
- g g
A B
z

_
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
nodal xy plane
88
Since atomic orbitals 2p
x
, and 2p
y
are linear combinations of atomic orbitals 2p
+1
and 2p
1
molec-
ular orbitals
u
2p
+1
and
u
2p
1
can be combined to construct molecular orbitals
u
2p
x
, and
u
2p
y
as follows,

u
2p
x
= 2p
x
(A) + 2p
x
(B),

u
2p
y
= 2p
y
(A) + 2p
y
(B).
Note, however, that molecular orbitals
u
2p
x
, and
u
2p
y
are not eigenfunctions of

L
z
.
The order of increasing energy for homonuclear diatomic orbitals is described by the following
diagram:

@
@
@
@

1s 1s

u
1s

g
1s

@
@
@
@

2s 2s

u
2s

g
2s

@
@
@
@

J
J
J
J
J
J

2p 2p

u
2p

g
2p

g
2p

u
2p
The electronic structure of homonuclear diatomic molecules can be approximated to zeroth order
by lling up the unperturbed states according to the Pauli exclusion principle. However, we should
always keep in mind that we are using the H
+
2
molecular orbitals (i.e., the unperturbed states) and,
therefore, we are neglecting the repulsive interaction between electrons.
This is the same kind of approximation implemented in the construction of zeroth order wave func-
tions of atoms according to hydrogenlike atomic orbitals, where the repulsion energy between elec-
trons was disregarded and the electronic conguration was constructed by lling up hydrogenlike
atomic orbitals according to the Pauli exclusion principle.
36.1 Exercise 55
(A) Predict the multiplicity of the ground state of O
2
.
(B) Show that the ground electronic state of C
2
is a singlet.
89
37 Conjugated Systems: Organic Molecules
The Hamiltonian of a molecule containing n electrons and N nuclei can be described according to
the Born-Oppenheimer approximation as follows,

H
el
=
n

i=1
_

2
2m
i

2
r
i

j=1
z
j
e
2
r
ji
_
+
n

i
n

k>i
e
2
r
ik
.
This Hamiltonian includes terms that describe both and electrons. However, the distinctive
chemistry of conjugated organic molecules is usually relatively independently of -bonds, and
rather correlated with the electronic structure of -electrons. For example, the spectroscopy of
conjugated organic molecules, as well as ionization potentials, dipole moments and reactivity, can
be described at least qualitatively by the electronic structure of the -electron model. Therefore,
we make the approximation that the solution of the eigenvalue problem of a conjugated system can
be factorized as follows,
=

A

,
where

A is an antisymmetrization operator upon exchange of and electrons.
The potential due to the nuclei and the average eld due to electrons, can be described by the
following Hamiltonian:

=
n

i=1

h
core
(i) +
n

i=1
n

k>i
e
2
r
ik
, (90)
where

h
core
includes kinetic energy of electrons, interaction of electrons with electrons,
and shielding of nuclear charges. An approximate solution can be obtained by disregarding the
repulsion between electrons in Eq. (90), and by approximating the Hamiltonian of the system as
follows,

H
(0)

i=1
H
eff
(i), where

H
eff
(j) =

2
2m
j

2
r
j

N

k=1
z

k
e
2
r
kj
. (91)
The effective nuclear charge z

k
incorporates the average screening of nuclear charges due to and
electrons.
Since

H
eff
(j) depends only on coordinates of electron j, we can implement the separation of vari-
ables method and solve the eigenvalue problem,

H
(0)

>= E

>,
according to the factorizable solution |

>=

n
j=1
|
j
>, where,

H
eff
(j) |
j
>=
j
|
j
> . (92)
The energy E

is obtained by using the Pauli exclusion principle to ll up the molecular orbitals,

after nding the eigenvalues
j
.
90
Eq. (92) is solved by implementing the variational method, assuming that |
j
> can be written
according to a linear combination of atomic orbitals,
|
j
>=
N

k=1
C
jk
|
k
>,
where |
k
> represents a 2p
z
orbital localized in atom k and the sum extends over all atoms in the
conjugated system.
Example:
Consider the ethylene molecule represented by the following diagram:
C C
H
H
H
H
1 2

_
The diagram shows bonds in the equatorial plane of the molecule, and orbitals 1 and 2 that are
perpendicular to such plane.
The LCAO for ethylene is,
|
j
>= c
j1
|
1
> +c
j2
|
2
> . (93)
Therefore, the secular equations can be written as follows,
(H
11
S
11

j
) c
j1
+ (H
12
S
12

j
) c
j2
= 0,
(H
21
S
21

j
) c
j1
+ (H
22
S
22

j
) c
j2
= 0.
H uckel Method:
The H uckel Method is a semi-empirical approach for solving the secular equations. The method
involves making the following assumptions:
1. H
kk
= , where is an empirical parameter (vide infra).
2. H
jk
= , when j = k 1; and H
jk
= 0, otherwise. The constant is also an empirical
parameter (vide infra).
3. S
jk
= 1, when k = j 1; and S
jk
= 0, otherwise.
91
According to the H uckel model, the secular determinant becomes,

j


j

= 0.
Therefore, the eigenvalues of the secular determinant are
j
= and can be represented by the
following diagram:
6
.. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..

Energy
E
2
= , |
2
>=
1

2
(|
1
> |
2
>)
E
1
= + , |
1
>=
1

2
(|
1
> + |
2
>)
E

= 2E
1
= 2 + 2, |

>=
1

2
|
1
(1) >|
1
(2) > ( ) .
The energy difference between ground and excited states is E = E
2
E
1
= 2. Parameter
is usually chosen to make E coincide with the peak of the experimental absorption band of the
molecule.
An interactive program to perform electronic structure calculations within the Simple Huckel
Molecular Orbital approximation can be found here.
A tutorial to perform electronic structure calculations and simulations of electronic dynamics
within the Extended Huckel Molecular Orbital method approximation can be found here.
38 Self-Consistent Field Hartree-Fock Method
The self-consistent eld (SCF) Hartree-Fock (HF) method is a variational approach for nding the
Slater determinant of a system of n-electrons,
| = |
1

2
...
n
(94)
that minimizes the expectation value of the energy:

E =
|

H|
|
,
92
for a xed nuclear conguration.
The one-electron basis functions
i
are typically expressed as linear combinations of spin or-
bitals
k
, as follows:

i
=

k
c
ki

k
, (95)
allowing for the variational approach to minimize

E with respect to the expansion coefcients c
ki
.
The energy is computed according to the usual Hamiltonian of a system of N nuclei and n
electrons, with a xed nuclear conguration:

H
el
=
n

i=1

h
(i)
+
n

i
n

k>i
e
2
r
ik
, (96)
where the spin-orbit coupling interactions are neglected. The rst term in Eq. (96) is the sum of
1-electron core Hamiltonians,

h
(i)
=

2
2m
e

2
r
i

j=1
z
j
e
2
r
ji
, (97)
describing a system of n non-interacting electrons in the electrostatic potential of the nuclei. The
second term in Eq. (96) is the sum of electron-electron interactions.
As a simple example, we consider the H
2
molecule with n = 2, N = 2 and r
1
, r
2
| =
2
1/2
(r
1
|
1
r
2
|
2
r
1
|
2
r
2
|
1
),
r
1
, r
2
|

H
el
| = 2
1/2
_
r
2
|
2
r
1
|

h
(1)
|
1
r
2
|
1
r
1
|

h
(1)
|
2
+r
1
|
1
r
2
|

h
(2)
|
2

r
1
|
2
r
2
|

h
(2)
|
1
+
e
2
r
12
[r
1
|
1
r
2
|
2
r
1
|
2
r
2
|
1
]
_
(98)
and the energy expectation value

E = |

H
el
|
=
1
2
_

1
|

h
(1)
|
1
+
2
|

h
(1)
|
2
+
2
|

h
(1)
|
2
+
1
|

h
(1)
|
1
+
+[
1

2
|
1

2
|]
e
2
r
12
[|
1

2
|
2

1
]
_
=
1
|

h
(1)
|
1
+
2
|

h
(1)
|
2
+
1
2
[
1

2
|
e
2
r
12
|
1

2
|
e
2
r
12
|
2

1

2

1
|
e
2
r
12
|
1

2
+
2

1
|
e
2
r
12
|
2

1
]
(99)
since

h
(1)
=

h
(2)
, according to Eq. (97). In general,

E =
n

j=1

j
|

h
(1)
|
j
+
1
2
n

j=1

k=j

k
|
e
2
r
12
|
j

k

j

k
|
e
2
r
12
|
k

j
, (100)
or

E =
n

j=1

j
|

h
(1)
|
j
+
1
2
n

j=1
n

k=1

k
|
e
2
r
12
|
j

k

j

k
|
e
2
r
12
|
k

j
, (101)
93
since
j

k
|
e
2
r
12
|
j

k

j

k
|
e
2
r
12
|
k

j
= 0, when j = k.
To minimize

E with respect to
j
, subject to the constraint of orthonormal orbitals, we apply
the Lagrange multiplier method for the following functional:
L(
1
, ...,
n
) =

E +

jk
[
j
|
k

jk
], (102)
where
jk
are the Lagrange multipliers. Varying the spin orbitals
j
in an innitesimal amount
j
,
with respect to the expansion coefcients c
kj
, we obtain:
L(
1
, ...,
n
) =

E +
n

j=1
n

k=1

jk
[
j
|
k
+
j
|
k
], (103)
where

E =

n
j=1

j
|

h
(1)
|
j
+
j
|

h
(1)
|
j

+
1
2

n
j=1

n
k=1

k
|
e
2
r
12
|
j

k
+
j

k
|
e
2
r
12
|
j

+
j

k
|
e
2
r
12
|
j

k
+
j

k
|
e
2
r
12
|
j

k
|
e
2
r
12
|
k

j

j

k
|
e
2
r
12
|
k

k
|
e
2
r
12
|
k

j

j

k
|
e
2
r
12
|
k

(104)
Substituting Eq. (104) into Eq. (103) and simplifying, we obtain:
L =

n
j=1

j
|

h
(1)
|
j
+

n
j=1

n
k=1

k
|
e
2
r
12
|
j

k

j

k
|
e
2
r
12
|
k

n
j=1

n
k=1

jk

j
|
k
+ c.c.
(105)
which gives,
L =

n
j=1

j
(1)|
_

h
(1)
|
j
(1) +

n
k=1

k
(2)|
e
2
r
12
|
k
(2)|
j
(1)

k
(2)|
e
2
r
12
|
j
(2)|
k
(1) +

n
j=1

n
k=1

jk
|
k

_
+ c.c. = 0
(106)
Since
j
is arbitrary, it must be that the expression in square brackets is equal to zero for all j:
_

h
(1)
+
n

k=1

k
(2)|
e
2
r
12
[1

P
12
]|
k
(2)
_
|
j
(1) =
n

j=1
n

k=1

jk
|
k
(107)
where the operator

P
12
permutes the states of electrons 1 and 2.
To write Eq. (107) in the canonical eigenvalue form, we change the basis set according to the
unitary transformation,
|

j
=

k
|
k

kj
, (108)
with

= 1. Considering that the Lagrange multipliers matrix is Hermitian (since the func-
tional L is real), it is always possible to nd a that diagonalizes according to the similarity
transformation:

(109)
94
Such a transformation denes the set of canonical spin orbitals |

j
for which

f
(1)
|

j
=

jj
|

j
. (110)
for j = 1 n, where

f
(1)
is the Fock operator,

f
(1)
=

h
(1)
+

V
HF
1
, (111)
where

V
HF
1
is the Hartree-Fock potential describing the electron-electron interactions, as follows:

V
HF
1
= J
1
(r
1
)

X
1
(r
1
), (112)
where J
1
(r
1
) is the Coulomb mean-eld potential,
J
1
(r
1
) =
n

k=1

k
|
e
2
r
12
|

k
. (113)
The matrix elements in Eq. (113) are integrals over the spatial and spin coordinates of electron 2.
Analogously,

X
1
(r
1
) is dened as the exchange operator,

X
1
(r
1
) =
n

k=j

k
(2)|
e
2
r
12

P
12
|

k
(2). (114)
Equation (110) denes a self-consistent eld (SCF) problem since the operator

f
(1)
, required
to nd the solutions

j
, depends on those functions through J
1
and

X
1
. To solve this SCF prob-
lem, we rst obtain approximate solutions

j
by approximating

f
(1)
by

h
(1)
(i.e., neglecting the
electron-electron interactions introduced by J
1
and

X
1
), or by using a semiempirical method (like
the Hueckel method described later in these lectures). These approximate functions

j
are then
used to compute J
1
and

X
1
, giving an approximate

f
(1)
that can be used to obtain improved func-
tions

j
. The process is repeated until convergence.
To solve the Hartree-Fock Eq. (110) by solving a set of matrix equations, we substitute

j
by
a linear combination of atomic orbitals, analogous Eq. (95): |

j
=

k
C
kj
|
k
. Making the
substitution and multiplying from the left with
k
|, we obtain:

k
|

f(j)|
k
C
kj
=
jj

k
|
j
C
kj
, (115)
or, in matrix form,
FC = SC

(116)
where we have introduced the overlap matrix S
jk
=
j
|
k
, the Fock matrix F
jk
=
j
|

f|
k
, and
the matrix of column eigenvectors C
kj
dening the canonical molecular orbitals

j
, with energies

jj
, expressed in the basis of atomic orbitals |
k
.
95