MO Theory

H2+ and H2 solns

Solutions to Hydrogen Molecule

Ion
2, E2 = -10.16 eV (for H2 )

1, E1 = 1.37 eV
(for H2)

Solutions to Hydrogen Molecule

MOs created from combinations of p-orbitals
pxA + pxB, pyA + pyB

pxA - pxB, pyA - pyB

pzA - pzB

pzA + pzB

Solutions to Hydrogen Molecule

px+ px OR py + py
px - px OR py - py

pz - pz
p z + pz

represents
center of
inversion

Parity

inversion

inversion

Gerade =
symmetric
with
inversion

Ungerade =
antisymmetric
with inversion

MO Energy Level Diagram for

Homonuclear Diatomics
lone atom

lone atom

2p

2p

*
2s

1s

2s

1s

Molecular Term Symbols

ML = (over all e )
identifies z-component of angular momentum
of an e Symbols used to id
-

| |

Molecular Term Symbols

Angular momentum about z-axis for all
electrons is M L
= |ML|
Symbol used to id

Molecular Term Symbols

Symbol is 2S + 1 g/u
2S + 1 is multiplicity as already used for atomic
term symbols
g or u identifies overall parity
To determine overall parity, make use of multiplication
of symmetric and antisymmetric functions

If the term is a term, a right superscript of + or

is added to indicate whether the wavefunction
is symmetric or antisymmetric with respect to
reflection through a plane containing the two
nuclei

Molecular Term Symbols

Remember sigma orbs:

From s orbs

From pz orbs

Remember pi orbs:

From px orbs

From py orbs

Molecular Term Symbols

Remember sigma-star orbs:

From s orbitals

From p orbitals

Remember pi-star orbs:

From px orbitals

From py orbitals

Spectroscopy Selection Rules

= 0, +1, -1
S = 0
note = Ms
= 0
note refers to spin-orbit coupling and

= 0, +1, -1

Molecular Term Symbols

Molecular Orbitals not always so clearcut
Remember how orbitals change energy as
go across PT
Can affect MO energy pattern too

MO Energy Level Diagram for

Homonuclear Diatomics
As you move
to the right on
PT, 2s and 2p
energy gap
increases.
Early, in the
period, then,
this permits
mixing of 2s
and 2pz
orbitals.
Atkins, Fig 14.30

Essentially LCAOs
involving four
orbitals are made.
The sigma orbitals
that we thought of
as being made by
the 2s orbitals are
lowered in E while
the sigma orbitals
that we thought of
as being made by
the 2pz orbitals are
raised in E.

MO Energy Level Diagram for Homonuclear

Diatomics (N2 and before)
lone atom

lone atom

2p
Use this
diagram for N2
and earlier in
PT
2s

1s

2p

2s

1s

Taking a look
at
heteronuclear
diatomic
molecules

Taking a look
at
heteronuclear
diatomic
molecules

MOs of HF
Unoccupied, E = -0.124 eV

Occupied, E = -0.3523 au

E = -0.491 au

E = -1.086 au

MOs of HF
H atom

H F molecule

F atom

1s

2p

2s

1s

Computational Chemistry
Considering complexity of the calculations weve been
doing, certainly, using computers to do these calcs
should be useful Computational Chemistry

For polyatomic molecules can make LCAOs MO

= cii
i constitute basis set (computational forms of atomic
orbitals)
Use variation theory to find ci
To find structure of molecule, must move nuclei and
find MOs find structure with lowest overall energy

Computational Chemistry
May solve for MOs using ab initio or semiempirical methods
Semi-empirical methods: empirical parameters
substituted for some integrals to save time in
calculations
Ab initio methods: supposedly make no assumptions
NOTE: computational chemistry may determine Energy
and some other properties without using quantum
chemistry
Such calculations are referred to as molecular
mechanics calculations

Valence Bond Theory

H2
Initial approx is = 1sA(1) 1sB(2)
But, is this a symm or antisymm wavefxn?

So, make LCs

= 1sA(1) 1sB(2) + 1sB(1) 1sA(2)
= 1sA(1) 1sB(2) - 1sB(1) 1sA(2)

In this case, turns out that + is lower E

Valence Bond Theory

Ground state wavefunction would be
bond = [1sA(1) 1sB(2) + 1sB(1) 1sA(2)][(1)(2) (2)(1)]

2 electrons in overlapping orbitals with

spins paired

Remember CH4
If try to make combinations of the valence s of C
with s of H, will be different type of wavefxn,
hence difft kind of bond than when make
combination of a p of C with an s of H
DONT see any diff in bonding of 4 Hs

Make LCs of valence orbitals on central atom

Call these LCs hybrid orbitals
Use these hybrid orbitals to make sigma bonds with H
Atomic orbitals NOT used to make sigma bonds used
to make pi bonds (Huckel method for conjugated)

Hybrid Orbitals
Valence s and p orbitals on C hybrids
1 = a12s + a22px + a32py + a42pz
= b12s + b22px + b32py + b42pz
= c12s + c22px + c32py + c42pz
= d12s + d22px + d32py + d42pz

Consider ethyne
Only two hybrids
1 = s + pz and y2 = s pz
Leftover px and py on one C overlap with px and py on
other C

Simplification to MO
Approach
Huckel Approach

Symmetry of Molecules

Determining Point Groups

Special Group?
No
Cn

No

C1

i
No

h
No
Yes

Yes

Cs

Ci
No

n v

No

Yes
Yes

No
Cn

Cnv

Yes

Cv , Dh , Td , Oh , Ih , Th

Yes

No

S2n or S2n and i only, collinear

with highest order Cn
Sn

Yes
nC2 perpendicular to Cn
Yes

Cnh
Dn No

No
n d
Yes

h
Yes

Dnh
Dnd

C2v Character Table

C2v

C2

v(xz)

v(yz)

A1

A2

-1

-1

B1

-1

-1

B2

-1

-1

Now go practice!!!

Applying Symmetry to MOs

Water

MOs of Water
HOMO-4
a1

Looks like s orbital on O, nbo

E = -18.6035 au

MOs of Water
HOMO-3 from two viewpoints
a1

Looks like s orbital

on O with
constructive
interference with
1 - bo

E = -0.9127 au

MOs of Water
HOMO-1

HOMO-2
b2

a1

Looks like combination of p on

O along C2 with constructive
interference with bo (close
to nbo)
E = -0.3356 au

Looks like combination of p on

O (perp to C2, but in plane of
molecule) with constructive
interference with bo
E = -0.4778 au

MOs of Water
HOMO from two viewpoints

b1
Looks like p orbital
on O, perpendicular
to plane of
molecule - nbo

E = -0.2603 au

MOs of Water
LUMO

LUMO +1
b2

a1

Looks like combination of p on

O along C2 with destructive
interference with abo
E = -0.0059 au

Looks like combination of p on

O (perp to C2, but in plane of
molecule) with destructive
interference with abo
E = 0.0828 au

Filling Pattern for Water

2b2 (abo)
4a1 (abo)
1b1 (nbo)
3a1 (bo/nbo)
1b2 (bo)
2a1 (bo)
1a1 (nbo)

Molecular Spectroscopy
Molecule has a number of motions
Translational, vibrational, rotational, electronic

Sum them to get total energy of molecule

Changes may occur in any of these
modes through absorption or emission of
energy
Vibrational: IR
Rotational: Microwave
Electronic: UV-Vis
CHP 16, 17, 18 of text

Statistical Mechanics
Quantum gives you possible energy levels
(states)
In a real sample, not all molecules in the same energy
level

With statistics and total energy, can predict (on

average) how many molecules in each state
Dynamic Equilibrium
Role of Temperature

Can predict macroscopic properties/behavior

Heat capacity, pressure, etc.
CHP 19, 20 of text