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8. APPLICATIONS TO MOLECULAR ORBITAL THEORY
L TH S NH
CHEMISTRY DEPARTMENT
NATURAL SCIENCES UNIVERSITY - HCM
2010
CHEMICAL USES OF SYMMETRY AND GROUP THEORY
1
Introduction
MO theory: study electronic structure,
bonding, and energy in molecules
There are many ways to treat the electronic
structure of molecules and their energy
In this chapter: emphasize the symmetry
aspect of the MO theory
Symmetry dont provide the relative energies
of these AO, MO
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LCAO Molecular Method
The simplest MO theory: molecular wave functions are
written as linear combinations of atomic wave functions
(LCAO: Linear Combinations of Atomic Orbitals)
where: f
i
: atomic wave functions
C
i
: coefficients
Note:
- Variation theorem: energy guessed from any Schrdinger
function (Y) will be higher than the true energy
- Molecular electronic wave functions are not really linear
combinations of atomic electronic wave functions
LCAO Molecular Method
The simplest MO theory: molecular wave functions
are written as linear combinations of atomic wave
functions (LCAO: Linear Combinations of Atomic
Orbitals)
Overlap of AOs MOs
Note:
- Number of generated molecular orbitals equals
number of initial atomic orbitals
- The molecular orbitals must have the same
symmetries as the composed atomic orbitals
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Summary of condition for AO overlap
AOs involve in the overlap must have:
Similar energy (when big difference in AO energies
insignificant bonding)
Same symmetry about the nuclear axis
AOs must be closed enough to provide good overlap of the
orbitals
If: - AOs are same sign in the overlap region bonding
- AOs are different sign in the overlap region antibonding
MO for the H
2
molecule: D
h
group
Two 1s orbitals of two H atoms involve in LCAO
Symmetry of these two 1s orbitals:
Symmetry of the two MO orbitals:
overlap of two 1s orbitals two MOs with s
g
+
and s
u
+
symmetry
D
h
E 2C

s
v
i 2S

C
2
G(1s) 2 2 2 0 0 0 = s
g
+
+ s
u
+
D
h
E 2C

s
v
i 2S

C
2
Y
b
1 1 1 1 1 1 = s
g
+
Y* 1 1 1 -1 -1 -1 = s
u
+
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Overlaps and energies of MOs
of the H
2
molecule
E
AO overlaps in the H
2
molecule
) 2 (
2 2 2 2
AB B A b
N Y Y Y Y
Y
b
= N (Y
A
+ Y
B
)
Y
*
= N (Y
A
Y
B
)
) 2 (
2 2 2 2 *
AB B A
N Y Y Y Y
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Experimental Observations:
Photoelectron Spectroscopy (PES)
Basis of the method: to
bornbard an atomic or
molecular species with
radiation of sufficient
energy to cause its
ionization
M(g) + hn M
+
(g) + e
(Photoelectron)
the energy balance being:
hn = I
M
+ DE
vib
+ DE
rot
+ E
k
e
Measure E
k
e raw PES
The PES of the H
2
molecule
The peak on the far right hand side of the
spectrum ionization energy of the H
2
molecule
Other additional peaks: due to vibration and
rotation of the molecule
Jack Barrett, Structure and Bonding, The Royal Society of Chemistry 2001
s Overlaps
s Overlap: (similar symmetry to the s orbital)
- cylindrical symmetry to rotation about the nuclear axis
- non-change sign when rotating about the nuclear axis
- s bonding: no nodal plane
z is the nuclear axis
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p Overlaps
p Overlap: (similar symmetry to the p orbital)
- change sign which C
2
rotation about the nuclear axis
- AOs are perpendicular to the nuclear axis
- p bonding: 1 nodal plane containing the nuclear axis
d Overlaps
d Overlap: (similar symmetry to the d orbital)
- change sign which C
4
rotation about the nuclear axis
- AOs plane are perpendicular to the nuclear axis
- d bonding: 2 nodal planes containing the nuclear axis
Note: antibonding always has an extra nodal plane perpendicular to
the nuclear axis
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Energies of 2s and 2p AO
of the second row
- B, C, N: small 2s-2p energy difference large 2s-2p interaction
- O, F: big 2s-2p energy difference small 2s-2p interaction
Energy levels of Homonuclear Diatomic Molecules
of the Second Period
s
p
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N
2
molecule: MO and PES spectrum
Figure 7.30 The PESs for the
diatomics N
2
, O
2
and F
2
.
Adapted with permission from
Brundle C.R. and Baker A.D.
(1977) Electronic Spectroscopy:
Theory, Techniques and
Applications, vol. 1, Academic
Press (ISBN 0-12-137801-2).
Copyright Elsevier.
D.J. Willock, Molecular Symmetry (Electronic version)
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Energy difference of ns-np of the elements Li-Kr
D.J. Willock, Molecular Symmetry (Electronic version)
MO: The Ligand Group Orbital approach (LGO)
For polyatomic molecules with a central atom and
other outer atoms (ligands): H
2
O, NH
3
, SF
6
,
[Co(NH
3
)
6
]
2+

Approach: molecular orbitals are constructed from:

(1) atomic orbitals of the central atom, and (2)
symmetry adapted combinations of ligand orbitals
(SAC or Ligand group orbitals, LGOs).
LGOs are formed by linear combination of the ligand
AOs:
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LGOs
MO: H
2
O molecule - C
2v
group
H
2
O: two s bonds only
Step 1: Find the
symmetry of the two s
bonds:
Reducible representation of the
two s bonds of H
2
O
G
s
s
v

s
v
0 2
Gs = A
1
+ B
2
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Step 2: Find AOs of oxygen to match with the symmetry
of the s bonds
From the character table:
A
1
: Os AO 2s, 2p
z
or a
1
orbitals
B
2
: 2p
y
b
2
orbital
Note: the 2p
x
of the oxygen does not involve in the construction
of the two s bonds.
Step 3: Construct the LGOs to match with the symmetry
of the s bonds
Linear combination of the two
1s of two H atoms 2 LGOs
with the A
1
and B
2
symmetry
LGO with A
1
symmetry:
LGO
1
= 1/2 (f
1
+ f
2
)
LGO with B
2
symmetry:
LGO
2
= 1/2 (f
1
- f
2
) +
+
+
+ +
_
_
_
J. Barrett, Structure and Bonding (electronic version)
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Pictorial overlap of a
1
orbitals
a
1
orbital of
Oxygen
LGO
1
orbital of
H (A
1
symmetry)
J. Barrett, Structure and Bonding (electronic version)
Pictorial overlap of b
2
orbitals
b
1
orbital of
Oxygen
LGO
2
of H
B
2
B
2
J. Barrett, Structure and Bonding (electronic version)
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Step 4:
The MO
diagram for
H
2
O
H
2
O
D.J. Willock, Molecular Symmetry (Electronic version)
MO diagram for H
2
O
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PES of H
2
O
MO for NH
3
: C
3v
group
Symmetry of the three s
bonds:
Irreducible representation
of the three s bonds:
G
s
=
C
3v
E 2C
3
3s
v
G
s
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The valence AOs of N involve
in the construction of MOs:
From the character table:
A
1
: Ns AO 2s, 2p
z
or a
1
orbitals
E: 2p
x
, 2p
y
e orbitals
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Construct the LGOs of H:
Take symmetry operations of s
1
orbital of H
1
in the
C
3v
group:
Dropping the repeating
C
3v
E C
3
C
3
2
s
v
s
v
s
v

s
1
s
1
s
2
s
3
s
1
s
2
s
3
C
3
E C
3
C
3
2
s
1
s
1
s
2
s
3
Construct the LGOs of H:
Projecting out the a
1
and e SALCs of the s
1
(H
1
atom):
LGOs of Hs orbitals:
LGO1 = 1/3 (s
1
+ s
2
+ s
3
)
LGO2 = 1/ 6 (2s
1
s
2
s
3
)
LGO 3 = 1/ 2 (s
2
s
3
)
C
3
E C
3
C
3
2
A
1
T
j
s
1
s
1
s
2
s
3
(s
1
+ s
2
+ s
3
)
ET
j
s
1
2s
1
s
2
s
3
(2s
1
s
2
s
3
)
ET
j
(s
2
s
3
) 2(s
2
s
3
) (s
3
s
1
) (s
1
s
2
) 2(s
2
s
3
)
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Figure 7.22
The MO
diagram for the
C
3v
molecule
NH
3
. For clarity,
the dotted lines
for the a
1
orbitals are
drawn in a
different style to
those for the
others.
D.J. Willock, Molecular Symmetry (Electronic version)
MO diagram for NH
3
CH
4
: T
d
group
Symmetry of the four s bonds:
G
s
Irreducible representation of the
four s bonds:
G
s
=
The orbitals of C with suitable
symmetry:
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Symmetry Adapted Linear Combinations of H orbitals
(LGOs)
A
1
symmetry T
2
symmetry
LGO of H:
(a
1
) = s
1
+ s
2
+ s
3
+ s
4

1
(t) = s
1
s
2
+ s
3
s
4

2
(t) = s
1
s
2
s
3
+ s
4

3
(t) = s
1
+ s
2
s
3
s
4
1
3
2
4
Pictorial overlap of the orbitals
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MO diagram for CH
4
Bond order = 4
For C H bond: 1
Figure 7.20: The MO diagram for CH
4
in the T
d
point group.
D.J. Willock, Molecular Symmetry (Electronic version)
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PES of the valence orbital region of CH
4
Figure 7.21: The PES of the valence orbital region of CH4. The original
spectra were reported in two sections (from 12 to 16.3 eV and from 21.9
to 24.2 eV ) and are bought together here on a single energy scale. The
vertical axis is photoelectron intensity in arbitrary units. Adapted from
Potts A.W., Price W.C. (1972) Proceedings of the Royal Society of London,
Series A 326: 165179. With permission from the Royal Society.
D.J. Willock, Molecular Symmetry (Electronic version)
Hypervalent molecules
Hypervalency: molecules (PF
5
, SF
6
and XeF
4
) which
the central main group element appears to expand
octet rule
Hypervalency has remained a controversial subject.
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Hypervalent molecule: SF
6
Symmetry of the six s bonds: O
h
group
Irreducible representation of the xis s
bonds:
G
s
= G
F
=
The orbitals of C with suitable symmetry:
Character Table of the O
h
group
Note:
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Central atom (S) LGOs of outer atoms
a
1g
t
1u
Symmetry Adapted Linear Combinations of
s orbitals of F (LGOs)
Symmetry Adapted Linear Combinations of
the s orbitals of F (LGOs)
e
g
orbitals
(non-bonding)
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MO diagram for SF
6
Electron configuration of SF
6
: (1a
1g
)
2
(1t
1u
)
6
(1e
g
)
4
The bond order: bond order = (8 0) = 4
or 4/6 = 2/3 per S-F
D.J. Willock, Molecular Symmetry (Electronic version)
Transition metal complexes:
-bonding in octahedral ML
6
complexes
LGOs of s bond of ligands:
AO of central atom:
a
1g
- s
e
g
- (d
z2
, d
x2-y2
)
t
1u
- (p
x
, p
y
, p
z
)
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MO diagram for ML
6
complexes (s bonds only)
-bonding in octahedral complexes
Two kinds of p bonding in
complexes:
donors (halides, OH
-
and O
2-
ligands): occupied AOs, usually
lone pairs, lower energy than the
metal orbitals
acceptors (such as CO, CN
-
,
C
2
H
4
): empty AOs, higher energy
than the metal orbitals
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Construct SALCs of the ligand -orbitals
Symmetry of the p bonding:
G
p
= T
1g
+ T
2g
+ T
1u
+ T
2u
(Can be calculated from: G
p
= G
bond
- G
s
)
AOs of metal can adapt the symmetry:
T
2g
AOs of M: (d
xy
, d
xz
, d
yz
): t
2g
T
1u
- (p
x
, p
y
, p
z
): t
1u
LGOs: t
2g
and t
1u
: form p bonds
t
1g
and t
2u
: from p non-bonds
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Examples
of the p
overlaps
MO diagram for ML
6
complexes: p donor
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MO diagram for ML
6
complexes: p acceptor
The frontier orbitals of Benzene
The highest energy atomic orbitals of benzene are the p
orbitals of benzene ring
Assume: the frontier MOs are composed of LCAO of the
C 2pp orbitals in D
6h
group:
Symmetry of the six C 2pp orbitals:
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D
6h
character Table
Construct the LCAOs by projecting out
the appropriate linear combination
D
6h
E C
6
C
3
C
2
C
3
2
C
6
5
A
2u
T
j
f
1
f
1
f
2
f
3
f
4
f
5
f
6
B
2g
T
j
f
1
f
1
f
2
f
3
f
4
f
5
f
6
E
1g
T
j
f
1
2f
1
f
2
f
3
2f
4
f
5
f
6
E
1g
T
j
(f
2
+ f
3
) 2f
2
+ 2f
3
f
3
+ f
4
f
4
f
5
2f
5
f
6
f
6
f
1
f
1
+ f
2
E
2u
T
j
f
1
2f
1
f
2
f
3
2f
4
f
5
f
6
E
2u
T
j
(f
2
f
3
) 2f
2
2f
3
f
3
+ f
4
f
4
+ f
5
2f
5
2f
6
f
6
+ f
1
f
1
+ f
2
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Construct the LCAOs by projecting out
the appropriate linear combination
D
6h
LCAO
A
2u
T
j
f
1
f
1
+f
2
+ f
3
+ f
4
+ f
5
+ f
6
B
2g
T
j
f
1
f
1
f
2
+ f
3
f
4
+ f
5
f
6
E
1g
T
j
f
1
2f
1
+ f
2
f
3
2f
4
f
5
+ f
6
E
1g
T
j
(f
2
+ f
3
) 3(f
2
+ f
3
f
5
f
6
)
E
2u
T
j
f
1
2f
1
f
2
f
3
+ 2f
4
f
5
f
6
E
2u
T
j
(f
2
f
3
) 3(f
2
f
3
+ f
5
f
6
)
Normalized LCAOs
YA
2u
1/6 (f
1
+f
2
+ f
3
+ f
4
+ f
5
+ f
6
) YB
2g
= 1/6 (f
1
f
2
+ f
3
f
4
+ f
5
f
6
)
YE
1g
a
= 1/12 (2f
1
+ f
2
f
3
2f
4
f
5
+ f
6
) YE
1g
b
= 1/2 (f
2
+ f
3
f
5
f
6
)
YE
2u
a
= 1/12 (2f
1
f
2
f
3
+ 2f
4
f
5
f
6
) YE
2u
b
= 1/2 (f
2
f
3
+ f
5
f
6
)
Pictorial presentation of LCAO
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The energy of the p MOs of benzene
based on the Hckel approximation
Energy diagram:
E
total
= 2(2b) + 4(b) = 8b (from quantum mechanics calculation)
The Ethene molecule: D
2h
group
Figure 7.33: The axis system and basis
used to obtain SALCs for the H(1s)
orbital set in the D
2h
molecule ethene.
Character Table of the D
2h
group
D.J. Willock, Molecular Symmetry (Electronic version)
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Ethene: Symmetry of the four H(1s)
D.J. Willock, Molecular Symmetry (Electronic version)
Ethene: Symmetry of the four H(1s)
Problems: Use the projection operator to obtain the
normalized SALC H(1s) functions and show that your answers
correspond to the orbital phase patterns above.
D.J. Willock, Molecular Symmetry (Electronic version)
a
g
b
1g
b
2u
b
3u
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Ethene: Symmetry of the C(2s,2p) orbitals
G(C(2s,2p)) = 2A
g
+ B
1g
+ B
2g
+ B
1u
+ B
2u
+ 2B
3u
D.J. Willock, Molecular Symmetry (Electronic version)
Ethene: Symmetry of the C(2s,2p) orbitals
G(C(2s,2p)) = 2A
g
+ B
1g
+ B
2g
+ B
1u
+ B
2u
+ 2B
3u
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Figure 7.34: The MO diagram for the ethene molecule
This figure shows the C
C energy levels in the D
2h
point group and in the
absence of the four H
atoms.
In this hypothetical
situation, the 1b
1u
and
1b
2u
MO have the same
energy, as do the 1b
1g
and 1b
2g
SALCs (similar
to the homonuclear
diatomics of C
2
)
D.J. Willock, Molecular Symmetry (Electronic version)
D.J. Willock, Molecular Symmetry (Electronic version)
Figure 7.35 shows the energy scheme for the C C bond in the ethene molecule with
the sp-hybridization formed the matched symmetry 2s and 2p
x
orbitals of C
Figure 7.35: The MO diagram for the ethene molecule
with the s-p hibridization
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Figure 7.36 The MO diagram for the D
2h
molecule ethene, using hybrid orbitals.
D.J. Willock, Molecular Symmetry (Electronic version)
Figure 7.36 brings together the C-C and
H(1s) SALCs to form the MO diagram of
ethane. It is found that the C-C orbitals
derived from p
y
have partners in the
H(1s) SALCs but those from p
z
orbitals
do not. Hence, the degeneracy expected
for the bonds in D
h
is lost.
- In the MO diagram of Figure 7.36 the H orbitals
are placed higher in energy than the bonding
SALCs of the C-C set since the electronegativity of
C is greater than H.
- Now there are 12 AO functions, and so there will
be 12 MOs formed. However, to keep the diagram
simple, only the six occupied valence orbitals and
two lowest unoccupied levels are shown.
- The first five orbitals contain bonding C-C and C-H
interactions, while the highest occupied level is the
bonding C-C 1b
1u
that is nonbonding for C-H.