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6/10/2013

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SIMPLE BONDING THEORY
INOCHE3 Lecture 2
Valence Bond Theory
treats the formation of a molecule as
arising from the bringing together of
complete atoms which, when they interact,
to a large extent, retain their original
character
All bonds are localized
Valence Bond Theory
electrons occupy atomic orbitals of
individual atoms within a molecule, and
that the electrons of one atom are
attracted to the nucleus of another atom.
At a minimum distance (where the electron
density begins to cause repulsion between
the two atoms) the lowest potential energy
is acquired, and is considered to be what
holds the two atoms together in a chemical
bond.
Features
Lewis electron-dot diagrams/Lewis
structures (Octet Rule)
Resonance hybrids when none of drawn
structures alone is adequate, lower energy
due to delocalization of electrons (bigger
box for particle in a box)
Features
Expanded shells or hypervalent atoms
Formal charges
VSEPR Theory
Steric number (number of electron pair
domains) is the number of positions occupied
by atoms or lone pairs around a central atom
lp-lp > lp-bp > bp-bp
Multiple bonds > single bonds
ClF
3
lp-lp 180 90 120 Cannot be determined
lp-bp 6 at 90 3 at 90
2 at 120
4 at 90
2 at 120
Cannot be determined
bp-bp 3 at 120 2 at 90
1 at 120
2 at 90 2 at 87.5
Axial Cl-F 169.8 pm
Equatorial Cl-F 159.8 pm
Cl
F
F
F
Cl
F
F
F Cl F
F
F
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C C
H
H
H
3
C
H
3
C
122.2
115.6
Electronegativity
Pauling bond energies
Mulliken EA and IE
Allred & Rochow attraction from Z*
Sanderson electron densities
Pearson EA and IE
Allen valence electron energies
Jaffe orbital electronegativities
Electronegativity and Angles
A more electronegative atom pulls bonding
electrons away from the central atom,
letting lone pairs spread out, resulting in
smaller angles
PF
3
< PCl
3
< PBr
3
OSF
2
< OSCl
2
< OSBr
2
Parallels size effects
Electronegativity and Angles
A more electronegative central atom pulls
bonding electrons toward itself increasing
concentration of electrons at the center,
bp-bp repulsions increase angles
H
2
O < H
2
S < H
2
Se
NCl
3
< PCl
3
< AsCl
3
When opposed
N(CH
3
)
3
110.9 < N(CF
3
)
3
117.9
Ligand Close Packing
Distance between outer atoms
(nonbonded) in molecules determine
molecular shapes
Molecule with the same central atom have
the nonbonded distances between outer
atoms constant with angles and lengths
changing.
Ligand Close Packing
VSEPR predicts NF
4
-
to have the bigger
angle (109.5 vs 102.3)
LCP predicts that FF distance is the same,
N-F bond is longer in NF
3
(136 vs 130)
N
F
F
F
F
N
F
F
F

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Polarity
Bonds between atoms of different
electronegativities are polar
Depending on the overall structure,
polarity of the bonds can result in
interactions between molecules
Dipole moments not always calculated by
adding vectors of bond moments
Qualitatively sufficient
Molecular Orbital theory
allocates electrons to molecular orbitals
formed by the overlap (interaction) of
atomic orbitals
Valence Bond Model in H
2

1
when atoms A and B are far apart,
electrons 1 and 2 have no interaction

2
when H atoms are close together,
impossible to tell which electron is
associated with which nucleus
) ( ) (
) ( ) (
...
1
...
2 1
2 1 cov
2
3
2
2
2
1
3 3 2 2 1 1 cov
spins parallel N
paired spin N
c c c
N
c c c
alent
alent



=
= + =
+ + +
=
+ + + =

+
Theoretical
d = 87 pm, U = 303 kJ mol
-1
Experimental
d = 74 pm; U = 458 kJ mol-1
Improvements:
electron screening (shielding)
Both electrons may be associated with
either nuclei:
H
A
+
H
B

or H
A

H
B
+
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3
,
4
for each of the ionic form
) ( [
)] ( ) [(
cov
4 3 2 1
ionic alent molecule
c N
c N


+ =
+ + + =
+
Theoretical
d = 75 pm, U = 398 kJ mol
-1
Experimental
d = 74 pm; U = 458 kJ mol
-1

1
H
A
(1)H
B
(2)

2
H
A
(2)H
B
(1)

3
[H
A
(1)(2)]

H
B
+

4
H
A
+
[H
B
(1)(2)]

H
2
is a resonance hybrid of the four
contributing resonance or canonical
structures
HH H
+
H

H
+
where each does not exist as a separate
species
each structure is also localized although
the combination (hybrid) as a whole may
be viewed as delocalized
MOT
Uses methods of group theory to describe
bonding in molecules
Symmetry properties and relative energies
of atomic orbitals determine how they
interact to form molecular orbitals
MOs are then filled with electrons
according to the same rules used for AOs
Total energy is then compared to gauge
stability
Pictorial Approach
Schrodinger equation for electrons in
molecules
Approximate solutions from linear
combination of atomic orbitals (LCAO),
sums and differences of atomic wave
functions
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H
2
= c
a

a
+ c
b

b
ls Lhe molecular wave funcLlon

a
and
b
are aLomlc wave funcLlons
- c
a
+ c
b
are ad[usLable coefflclenLs (equal or unequal,
poslLlve or negaLlve)
- CrblLals overlap when dlsLance beLween aLoms
decrease wlLh slgnlflcanL probablllLy for elecLrons
from boLh aLoms ln Lhe reglon of overlap
- LlecLrons ln bondlng MCs occupy Lhe space
beLween nuclel
Conditions
Symmetry of orbitals must be such that
regions with the same sign of overlap
Energies of the atomic orbitals must be
similar (large differences in energies result
in small changes in MO energies
compared with the AOs)
Distance between the atoms must be short
enough to provide good overlap of orbitals
but not too short for repulsions to interfere
MOs from s orbitals
- ln general
() = [c
a

a
(1
a
) + c
b

b
(1
b
)]
() = [c
a

a
(1
a
) - c
b

b
(1
b
)]
- n ls Lhe normallzlng facLor so
- lor P
2
[ ] ) ( ) 1 ( ) 1 (
2
1
) (
b a b a
H H s s + + =
[ ] ) ( ) 1 ( ) 1 (
2
1
*) (
b a b a
H H s s =
}
= 1 * d
MO Types
Bonding molecular orbitals result in
increased concentration of electrons
between two nuclei and has lower energy
than starting atomic orbitals
Antibonding orbitals results in nodes with
zero electron density between nuclei
caused by cancellation of the wave
functions and has higher energy
MO Diagram
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More precise calculations show
coefficients of * are slightly larger than for
orbital
orbitals
Orbitals symmetric to rotation about the
bond axis are designated orbitals
Antibonding orbitals are indicated with an
asterisk * in simpler cases where bonding
and antibonding characters are clear
The number of resulting MOs is the same
as the initial number of AOs in the atoms
MOs from p orbitals MOs from p orbitals
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orbitals
The notation for MOs indicates a change
in sign with C
2
(180) rotation about the
bond axis
Nodes of atomic orbitals become the
nodes of the resulting MOs
antibonding case MO is similar in
appearance to an expanded d orbital
MOs from d orbitals
orbitals
When atomic orbitals from two parallel
planes and combine side to side they form
orbitals
The notation indicates sign changes on
C
4
rotation (90)
orbitals have no node, orbitals have
one node, orbitals have two nodes (that
include the bond axis)
Nonbonding Orbitals
MOs whose energies are essentially that
of the original atomic orbitals
When three atomic orbitals satisfy the
requirement for MO formation
When atomic orbital symmetries do not match
When atomic orbitals have quite different
energies (1s and 2s)
Homonuclear Diatomic
Molecules
Assuming interactions
only between AOs of
identical energies,
second period
diatomic molecules
share the general
pattern of MOs
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General Rules
The number of molecular orbitals = the
number of atomic orbitals combined
Of the MO's, half are bonding (lower energy)
and the other half are anti-bonding (higher
energy)
Electrons enter the lowest orbital available
The maximum number of electrons in an
orbital is 2 (Pauli Exclusion Principle)
Electrons spread out before pairing up
(Hund's Rule)
Bond Order
Overall number of bonding and
antibonding electrons determine the bond
order (number of bonds)
MOs from the 1s orbitals have no net
effect on bonding (inner orbitals)
(

|
|
.
|

\
|

|
|
.
|

\
|
=
orbitals g antibondin in
electrons of number
orbitals bonding in
electrons of number
order Bond
2
1
Molecule Bond
Order
Bond
Energy,
eV
Bond
Length,
O
2
2 5.12 1.21
F
2
1 1.60 1.41
Ne
2
0 Molecule not
observed
Orbital Mixing

g
(2s) orbital interacts
with the
g
(2p
z
) orbital

u
*
(2s) orbital interacts
with the
u
*
(2p
z
) orbital
Hybridization/mixing
Change in the relative
energies of the
molecular orbitals
B
2
, C
2
, and N
2
are best
described by a model
that includes
hybridization
Four MOs result from combining four atomic
orbitals (two 2s, and two 2p
z
) that have
similar energies and appropriate symmetries
c
1
= c
2
; c
3
= c
4
for homonuclear molecules
Lowest E MO have larger c
1
and c
2
Highest E MO have larger c
3
and c
4
Same symmetries but higher E for upper two
and lower E for two lower orbitals
) 2 ( ) 2 ( ) 2 ( ) 2 (
4 3 2 1 b a b a
p c p c s c s c =
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Homonuclear Diatomic
Molecules
Period 2 Molecular Configurations
Correlation Diagrams
Shows calculated effect of moving two atoms
together from infinite separation to zero
interatomic distance (merged/united atom)
As atoms move closer, MOs form
At still smaller separation, bonding MOs decrease
in energy while antibonding MOs increase
At 0 separation, MOs become AOs of united atom
Actual energies of MOs are intermediate
between extremes
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Noncrossing Rule
Orbitals of the same symmetry interact so
their energies never cross
Heteronuclear Diatomic MOs
Follow the same general bonding pattern as
homonuclear
Greater nuclear charge on one atom lowers
its atomic energy levels and shifts the
resulting molecular orbital levels
(electronegative atom)
Different atomic orbital energies result in
MOs with unequal contributions from the AOs
AO closer in energy to an MO contributes
more to the MO (larger c
i
)
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Carbon monoxide
Frontier Orbitals
Highest occupied molecular orbital, HOMO
Lowest unoccupied molecular orbital,
LUMO
CO chemistry with transition metals
M-O-C vs M-C-O
HOMO has larger electron density on
carbon because O 2p
z
contributes to more
MOs than C 2p
z
Ionic Compounds
As an ion pair, limiting form of polarity in
heteronuclear diatomic molecules
Concentration of electrons shifted to the
more electronegative atom until it is
transferred completely
Ionic Compounds Li
+
F
-
Combination of electrostatic attraction and
non-directional covalent bonding
Formation as a sequence of elementary
steps:
Li (s) Li (g)
Li (g) Li
+
(g) + e
-
F
2
(g) F (g)
F (g) + e
-
F
-
(g)
Li
+
(g) + F
-
(g) LiF (g)
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MO theory applied to H
2
Nuclei are placed in their equilibrium
positions then MOs are calculated for the
electrons to occupy
MO arises from atomic orbitals interactions
If the symmetries of the atomic orbitals are
compatible
If the region of overlap between atomic
orbitals is significant
If the interacting atomic orbitals are relatively
close in energy
The number of MOs that can be formed
must equal the number of atomic orbitals
of the constituent atoms
MOs have associated energies and
electron distribution follow aufbau principle
MO (in-phase)
MO = N [
1
+
2
]
MO (out-of-phase)
*MO = N* [
1

2
]
2
1
) 1 ( 2
1
*
2
1
) 1 ( 2
1

+
=
S
N
S
N
is used to label orbitals that generates no
phase change when rotated about the
internuclear axis
* is used when there is a nodal plane
between the nuclei and this plane is to
the internuclear axis. The lack of electron
density on the nodal plane raises
internuclear repulsion and destabilizes the
MO, making it antibonding
Bond order = [(number of bonding
electrons) (number of antibonding
electrons)]
General result of MO is delocalized
bonding character over the molecular
framework
POLYATOMIC MOLECULES
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Orbital Hybiridzation
Mixing
Model
Derived spatially directed orbitals for the VB
Theory (localized -bonds)
One hybridization scheme is appropriate for an
atom X in a molecule XYn of a particular shape
Labeled to reflect contributing atomic orbitals
Generated by mixing the characters of atomic
orbitals
sp Hybridization
Linear species, BeCl2 with equivalent Be-
Cl bonds
One s atomic orbital and one p atomic
orbital
n atomic orbitals produce n hybrid orbitals
( )
( )
p s sp
p s sp
2 2
2 2
2
1
2
1


=
+ =
sp
2
Hybridization
Trigonal planar species, BH
3
with
equivalent B-H bonds
y x
y x
x
p p s
sp
p p s
sp
p s
sp
2 2 2
2 2 2
2 2
2
1
6
1
3
1
2
1
6
1
3
1
3
2
3
1
2
2
2



=
+ =
+ =
sp
3
hybridization
Tetrahedral and related species
) (
2
1
) (
2
1
) (
2
1
) (
2
1
2 2 2 2
2 2 2 2
2 2 2 2
2 2 2 2
3
3
3
3
z y x
z y x
z y x
z y x
p p p s
sp
p p p s
sp
p p p s
sp
p p p s
sp




+ =
+ =
+ =
+ + + =
Other schemes
sp
3
d (dz
2
) trigonal bipyramidal
sp
3
d (dx
2
-y
2
) square-based pyramidal
sp
3
d
2
octahedral
sp
2
d square planar
MO Theory: Ligand Group Orbitals
different treatment for polyatomic
molecules
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Linear XH
2
two 1s orbitals are taken as a group, the ligand
group orbital (LGO)
transforming description from atomic orbitals of
X and H to atomic orbitals of X and LGOs of
H - - - H
the number of LGOs formed = the number of
atomic orbitals used
to generate the other LGOs, consider phases of
separate orbitals (bonding and antibonding
sense)
The MO is then constructed from the
interaction (symmetry consideration) of the
valence atomic orbitals of X and the LGO
of H - - - H
Group theory simplifies the selection of
LGOs for larger molecules
Starting from identification of point group
Only ligand group orbitals that can be
classified within the point group of the whole
molecule are allowed
FHF
-
Linear ion with D
h
symmetry, which is
simplified with D
2h
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1 x
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
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E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1 1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1 1 1 1
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E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1 1 1 1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1 1 1 1 1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 1 1 1 1 1 1
A
g
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1
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E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1 -1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1 -1 -1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1 -1 -1 -1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1 -1 -1 -1 1
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1 -1 -1 -1 1 1
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D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1 x
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1 x
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz)
1 1 -1 -1 -1 -1 1 1
B
1u Atomic orbitals and group orbitals of the
same symmetry can combine to form
molecular orbitals
In this case there are two A
g
LGOs
Energy match of the 1s orbital of H (-13.6
eV) is better with the 2p
z
(-18.7 eV) than
the 2s (-40.2 eV) of fluorine
Polyatomic MO diagrams: central atom
orbitals on the left, and group orbitals on
the right, with MOs in the middle
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Lewis approach requires two electrons to
represent a single bond between two
atoms: F-H-F (?)
MO: two electrons in a bonding MO
formed by the interaction of all three atoms
For the similarly linear CO
2
the same set of
group orbitals are formed by the two
oxygens, but the interactions with C now
include p orbitals
B
3u
B
2u
A
g
A
g
B
2g
B
3g
B
1u
B
1u
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1 x
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1 x
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B
3u
B
2u
A
g
A
g
B
2g
B
3g
B
1u
B
1u
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1
z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1 x
B
3u
B
2u
A
g
A
g
B
2g
B
3g
B
1u
B
1u
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1
y
B
3u 1 -1 -1 1 -1 1 1 -1 x
B
3u
B
2u
A
g
A
g
B
2g
B
3g
B
1u
B
1u
D
2h
E C
2
(z) C
2
(y) C
2
(x) i (xy) (xz) (yz) _ _
A
g 1 1 1 1 1 1 1 1 x
2
; y
2
; z
2
B
1g 1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g 1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g 1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u 1 1 1 1 -1 -1 -1 -1
B
1u 1 1 -1 -1 -1 -1 1 1 z
B
2u 1 -1 1 -1 -1 1 -1 1 y
B
3u 1 -1 -1 1 -1 1 1 -1
x
6/10/2013
21
B
3u
B
2u
A
g
A
g
B
2g
B
3g
B
1u
B
1u
Orbital energies
Orbital 2s 2p
Carbon -19.4 eV -10.7 eV
Oxygen -32.4 eV -15.9 eV
a
g
() 2s -2s (-32.4) with 2s (-19.4) b
1u
(non) 2s -2s (-32.4) with 2s (-19.4)
a
g
() 2p
z
-2p
z
(-15.9) with 2s (-19.4) b
1u
() 2p
z
-2p
z
(-15.9) with 2p
z
(-10.7)
6/10/2013
22
b
3u
and b
2u
() 2p
x
-2p
x
(-15.9)
with 2p
x
(-10.7)
b
2g
and b
3g
(non) 2p
x
-2p
x
and 2p
y
-2p
y
b
3u
and b
2u
(2p
x
-2p
x
with 2p
x
a
g
(*) 2p
z
-2p
z
with 2s
b
1u
(*) 2p
z
-2p
z
with 2p
z
H
2
O, C
2v
Take the H
2
O molecule as lying in the yz
plane
C
2v
character table
C
2v
E C
2
(z)
v
(xz)
v
(yz)
A
1
+1 +1 +1 +1
A
2
+1 +1 -1 -1
B
1
+1 -1 +1 -1
B
2
+1 -1 -1 +1
6/10/2013
23
2s orbital of O in H
2
O: A
1
E C
2

v
(xz)
v
(yz)
1 1 1 1
2p
x
orbital: B
1
E C
2

v
(xz)
v
(yz)
1 -1 1 -1
2p
y
orbital: B
2
E C
2

v
(xz)
v
(yz)
1 -1 -1 1
2p
z
orbital: a
1
E C
2

v
(xz)
v
(yz)
1 1 1 1
labels in the first column are the symmetry
types of orbitals that are permitted within
the point group
numbers in the column headed E indicate
the degeneracy of each type of orbital in
the point group
each row of numbers following a given
symmetry label indicates how a particular
orbital behaves when operated on by each
symmetry operation. A number 1 indicates
the orbital is unchanged by the operation,
a 1 means that the orbitals changes sign,
and a 0 means that the orbital changes in
some other way.
6/10/2013
24
systematic reduction of reducible
representations

=
c
r i c
g
h
n
1
Tabular Method
4

h
C
2v
E C
2

v
(xz)
v
(yz
)

2 0 0 2
A
1
2 0 0 2 4 1
A
2
2 0 0 2 0 0
B
1
2 0 0 2 0 0
B
2
2 0 0 2 4 1
E C
2

v
(xz)
v
(yz)
2 0 0 2
A
1
1 1 1 1
B
2
1 1 1 1
only two LGOs can be constructed (from
the two 1s orbitals)
the symmetry of the LGO must correspond
to one of the symmetry types in the
character table
= A
1
+ B
2
the LGOs must possess a
1
and b
2
symmetries
H- - -H LGO: A
1
E C
2

v
(xz)
v
(yz)
2 0 0 2
6/10/2013
25
If the two 1s orbitals
of the Hs are
designated
1
and
2
and the operations of
the group are applied
on one of the orbitals
E C
2

v
(xz)

v
(yz)

1

2

2

1
The composition of the a
1
LGO is obtained
by multiplying the corresponding A1
character with each of the functions
obtained:
(a1) = (1
1
) + (1
2
) + (1
2
) + (1
1
)
= 2
1
+ 2
2
in-phase combination
the b2 LGO is obtained by multiplying the
corresponding B
2
characters:
(b
2
) = (1
1
)+(1
2
) + (1
2
) +
(1
1
)
= 2
1
2
2
out-of-phase combination
2s and 2p both have a1 symmetry and
could interact with a1 LGO forming three
MOs: two bonding and one anti-bonding.
The lowest energy a1 is dominated by 2s
contribution because of the separation of
2pz.
BH
3
z axis coincides with the C
3
, all atoms lie
in the xy plane
D
3h
6/10/2013
26
D
3h
E 2C
3
3C
2

h
2S
3
3
v
A'
1
1 1 1 1 1 1 x
2
+y
2
; z
2
A'
2
1 1 -1 1 1 -1 R
z
E' 2 -1 0 2 -1 0 (x;y) (x
2
-y
2
;xy)
A''
1
1 1 1 -1 -1 -1
A''
2
1 1 -1 -1 -1 1 z
E'' 2 -1 0 -2 1 0 (R
x
;R
y
) (xz;yz)
Examination of the last two columns of
character tables give symmetry behavior
of orbitals on the central atom in the point
group:
2s a1
2p
z
a2
2p
x
and 2p
y
e
For the 3H LGOs
12

h
D
3h
E 2C
3
3C
2

h
2S
3
3
v

3 0 1 3 0 1
A
1
3 0 3 3 0 3 12 1
A
2
3 0 3 3 0 3 0 0
E 6 0 0 6 0 0 12 1
A
1
3 0 3 3 0 3 0 0
A
2
3 0 3 3 0 3 0 0
E 6 0 0 6 0 0 0 0
LGO symmetries: a1 + e ( combination
generated by application of projection
operators)
D
3h
E 2C
3
3C
2
s
h
2S
3
3s
v
a
1

1

2

3

1

1

2

2
(a
1
) = 4
1
+ 4
2
+ 4
3

1
+
2
+
3
=
(e
1
)
1
=
(e
1
)
2
=
*from consideration of degeneracy number
of nodes and orthogonality
) (
3
1
3 2 1
+ +
) 2 (
6
1
3 2 1

) (
2
1
3 2

6/10/2013
27
T
d
Symmetry elements for the
group
Spectroscopy active component
E 8C
3
3C
2
6S
4
6
sd
Microwave IR Raman
A
1
1 1 1 1 1 x
2
+y
2
+z
2
A
2
1 1 +1 -1 -1
E 2 -1 2 0 0
(2z
2
-x
2
-y
2
,
x
2
-y
2
)
T
1
3 0 -1 1 -1 (R
x
, R
y
, R
z
)
T
2
3 0 -1 -1 1 (x, y, z) (xy, xz, yz)
D
3h
Symmetry elements for the group Spectroscopy active component
E
2C
3
(z)
3C'
2

h
(xy)
2S
3
3
v
Microwa
ve
IR Raman
A'
1
1 1 1 1 1 1
x
2
+y
2
,
z
2
A'
2
1 1 -1 1 1 -1 R
z
E' 2 -1 0 2 -1 0 (x, y)
(x
2
-y
2
,
xy)
A''
1
1 1 1 -1 -1 -1
A''
2
1 1 -1 -1 -1 1 z
E'' 2 -1 0 -2 1 0 (R
x
, R
y
) (xz, yz)
D
2h
Symmetry elements for the group Spectroscopy active component
E
C
2
(z)
C
2
(y)
C
2
(x)
i
(xy)

(xz)

(yz)
Microw
ave
IR Raman
A
g
1 1 1 1 1 1 1 1 x
2
, y
2
, z
2
B
1g
1 1 -1 -1 1 1 -1 -1 R
z
xy
B
2g
1 -1 1 -1 1 -1 1 -1 R
y
xz
B
3g
1 -1 -1 1 1 -1 -1 1 R
x
yz
A
u
1 1 1 1 -1 -1 -1 -1
B
1u
1 1 -1 -1 -1 -1 1 1 z
B
2u
1 -1 1 -1 -1 1 -1 1 y
B
3u
1 -1 -1 1 -1 1 1 -1 x
O
h
Symmetry elements for the group
E 8C3 6C2 6C4 3C2 =(C4)2 i 6S4 8S6 3 h 6 d IR Raman
A1g 1 1 1 1 1 1 1 1 1 1 x
2
+y
2
+z
2
A2g 1 1 -1 -1 1 1 -1 1 1 -1
Eg 2 -1 0 0 2 2 0 -1 2 0 (2z
2
-x
2
-y
2
, x
2
-y
2
)
T1g 3 0 -1 1 -1 3 1 0 -1 -1
T2g 3 0 1 -1 -1 3 -1 0 -1 1 (xz, yz, xy)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 -1 -1 1 -1 1 -1 -1 1
Eu 2 -1 0 0 2 -2 0 1 -2 0
T1u 3 0 -1 1 -1 -3 -1 0 1 1 (x, y, z)
T2u 3 0 1 -1 -1 -3 1 0 1 -1

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