Polyatomic Molecular

Orbital Theory

Transformational properties of atomic orbitals

• When bonds are formed, atomic orbitals combine according to their

symmetry.

• Symmetry properties and degeneracy of orbitals and bonds can be learned

from corresponding character tables by their inspection holding in mind the
following transformational properties:

Atomic orbital Transforms as

S
s x2+y2+z2
px x
py y py
pz z
dz2 z2, 2z2-x2-y2
dx2-y2 x2-y2
dxy xy dz2
dxz xz
dyz yz

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 Examples of atomic orbitals symmetry analysis
C2v
Atomic orbital Mulliken labels
A1 z x2, y2, z2
C2v D3h D4h Td Oh
A2 Rz xy
s a1 a 1' a1g a1 a1g
B1 x, Ry xz
px b1 e' eu t2 t1u
B2 y, Rx yz
py b2 e' eu t2 t1u
a1 a 2" a2u t2 t1u D3h
pz
a1 a 1' a1g e eg A1’ x2+y2, z2
dz2
A2’ Rz
dx2-y2 a1 e' b1g e eg
t2g E’ (x,y) (x2-y2, xy)
dxy a2 e' b2g t2
t2g A1”
dxz b1 e" eg t2
A2” z
dyz b2 e" eg t2 t2g
E” (Rx,Ry) (xz, yz)

D4h Td Oh
A1g x2+y2, z2 A1 x2+y2+z2 A1g x2+y2+z2
B1g x2-y2 A2 Eg (2z2-x2-y2, x2-y2)
B2g xy E (2z2-x2-y2, x2-y2) T1g (Rx,Ry,Rz)
Eg (Rx,Ry) (xz, yz) T1 (Rx,Ry,Rz) T2g (xz, yz, xy)
A2u z T2 (x,y,z) (xz, yz, xy) T1u (x,y,z)
Eu (x, y) …

MO diagram of homonuclear diatomic molecules

• Filling the resulting MO’s of homonuclear

diatomic molecules with electrons leads to the
following results: A B
6σu

2πg
AB # of e’s Bond # Bond 2p 2p
order unpair. energy, 5σg
e’s eV
1πu
Li2 6 1 0 1.1
Be2 8 0 0 - 4σu
2s 2s
B2 10 1 2 3.0
C2 12 2 0 6.4 3σg
N2 14 3 0 9.9
O2 16 2 2 5.2 2σu
1s 1s
F2 18 1 0 1.4
1σg
Ne2 20 0 0 -

Bond order = ½ (#Bonding e’s - #Antibonding e’s)

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 MO-energy levels in N2 molecule
• Photoelectron spectroscopy of simple molecules is an invaluable source of the
information about their electronic structure.

• The He-I photoelectron spectrum of gaseous N2 below proves that there is the σ-π level
inversion in this molecule. It also allows identify bonding (peaks with fine vibronic
structure) and non-bonding MO (simple peaks) in it.

N N
6σ u

2π g
2p 2p
15.6 5σ g
16.7
1π u
18.8
4σu
2s 2s

3σ g

E, eV 2σ u
1s 1s
1σ g

Let’s Play with some MO’s

water…water…water….

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 To begin….How to Deal with more
than two atoms?
You use some Acronyms! Sounds Good!

• SALCs – Symmetry Adapted Linear

Combinations

• LGOs – Ligand Group Orbitals

Lets Separate the O for the H H

Oxygen

Hydrogen

To the Character Tables

Ha Hb

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 z

O x
H H
y

O (py) Oxygen
B2

O (px) B1

O (pz)

A1
O (s)

O x
H H
y

Ha - Hb (s) Hydrogen

B1

Ha + Hb (s)

A1

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 NOW Let’s Make Some MOs
LGOs

B1

A1

A1

Oxygen Hydrogens

NOW Let’s Make Some MOs

LGOs

B2
4 A1

A1

3 A1

A1
2 A1

Oxygen Hydrogens

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 NOW Let’s Make Some MOs
LGOs

B2
4 A1

A1

3 A1

A1
2 A1

Oxygen Hydrogens

NOW Let’s Make Some MOs

LGOs
2 B1
B1

A1
1B2

1B1

A1

Oxygen Hydrogens

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 NOW Let’s Make Some MOs
LGOs
2 B1
B1

A1
1B2

1B1

A1

Oxygen Hydrogens

NOW Let’s Make Some MOs

LGOs
2 B1
B1
4 A1

A1
1B2

3 A1

1B1

A1
2 A1

Oxygen Hydrogens

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 NOW Let’s Make Some MOs
LGOs
2 B1
B1
4 A1

A1
1B2

3 A1

1B1

A1
2 A1

Oxygen Hydrogens

Now for the Million Dollar

Question
Why is Water Bent???

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 Molecular Orbital Theory – linear XH2 molecules

Molecular Orbitals of BeH2

• BeH2 (D∞h) 2H
Be
H Be H 5σ
σu
σu+
z
s-s
y
4σ
σg

Group orbitals of 2H's:

πu 2.2 eV -13.5 eV
2px 2py
πu s+s
ψs - ψs 2pz σu+ σg+

σg+
ψs + ψs 2s 3σ
σu

-8.2 eV
1σg22σg23σu2
2σ
σg

D∞h ∞σv i
1s
Σg+ 1 1 x2+y2, z2 1σ
σg
-128 eV
Σu+ 1 -1 z
Πu 0 -2 (x,y)

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 Molecular Orbital Theory – Walsh diagram

The Walsh diagram

shows what happens to
the molecular orbitals for
a set of molecules which
are related in structure.
In this case, the
difference is the H-X-H
bond angle which
decreases from 180o to
90o

Molecular Orbital Theory – Walsh diagram

H O
Water
104.5° H H

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 4) MO theory and molecular geometry (Walsh diagrams)

• Correlate changes in energy of MO’s between species ABx of high

and lower symmetry, such as BeH2 and H2O.

z
5σ
σu
O
H H 2b2

y 4a1
x
4σ
σg

πu b1

BeH2 2σg23σu2 linear 3a1

BH2 2a121b223a11 , 131o

CH2 2a121b223a12 , 102o
1b2
NH2 2a121b223a121b11 , 103o 3σ
σu
OH2 2a121b223a121b12 , 105o
FH2+ 2a121b223a121b12 , 113o
2σ
σg
2a1

Molecular Orbital Theory – BH3

BH3 has a C3 principal axis of symmetry, 3 C2 axes (┴ C3), 3 σv,

and σh – it is in a D3h point group

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 Molecular Orbital Theory – BH3

The BH3 molecule exists in the gas phase,

but dimerizes to B2H6 (which we will look at a
bit later)
z
2 BH3 B2H6

The BH3 molecule is trigonal planar and we H

B H y
will make the C3 principal axis of symmetry
the z axis, with the x and y axes in the plane H
of the molecule. The y axis (arbitrary) will be
along one of the B-H bonds. x

Molecular Orbital Theory – D3h Character Table

D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1
A2’ 1 1 -1 1 1 -1
E’ 2 -1 0 2 -1 0
A1” 1 1 1 -1 -1 -1
A2” 1 1 -1 -1 -1 1
E” 2 -1 0 -2 1 0

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 Molecular Orbital Theory – D3h Character Table

D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1

A2’ 1 1 -1 1 1 -1

E’ 2 -1 0 2 -1 0

A1” 1 1 1 -1 -1 -1

A2” 1 1 -1 -1 -1 1

E” 2 -1 0 -2 1 0

Molecular Orbital Theory – D3h Character Table

D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1 2s

A2’ 1 1 -1 1 1 -1

E’ 2 -1 0 2 -1 0

A1” 1 1 1 -1 -1 -1

A2” 1 1 -1 -1 -1 1

E” 2 -1 0 -2 1 0

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 Molecular Orbital Theory – D3h Character Table

D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1

A2’ 1 1 -1 1 1 -1

E’ 2 -1 0 2 -1 0

A1” 1 1 1 -1 -1 -1

A2” 1 1 -1 -1 -1 1 2pz

E” 2 -1 0 -2 1 0

Molecular Orbital Theory – D3h Character Table

D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1

A2’ 1 1 -1 1 1 -1

E’ 2 -1 0 2 -1 0

A1” 1 1 1 -1 -1 -1

A2” 1 1 -1 -1 -1 1
2px 2py
E” 2 -1 0 -2 1 0
doubly degenerate

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 Molecular Orbital Theory – D3h Character Table

D3h E 2C3 3C2 σh 2S3 3σv

A1’ 1 1 1 1 1 1

A2’ 1 1 -1 1 1 -1

E’ 2 -1 0 2 -1 0

A1” 1 1 1 -1 -1 -1

A2” 1 1 -1 -1 -1 1

E” 2 -1 0 -2 1 0

Molecular Orbital Theory – LGOs on H atoms

In BH3 we need three LGOs, formed from linear combinations of

the H 1s orbitals
H

H H
What happens if we carry out the D3h symmetry operations on
this group of H 1s orbitals? How many remain unchanged?

E C3 C2 σh S3 σv

3 0 1 3 0 1

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Molecular Orbital Theory – LGOs on H atoms

E C3 C2 σh S3 σv

3 0 1 3 0 1

The resulting row of characters is also obtained by adding the

characters of the A1’ and E’ representations

D3h E 2C 3C σh 2S 3σ
3 2 3 v
A1’ 1 1 1 1 1 1
E’ 2 -1 0 2 -1 0
LGOs 3 0 1 3 0 1

Molecular Orbital Theory – LGOs for BH3

Ψ(a1’) = (1/√3)(Ψ1 + Ψ2 + Ψ3)

Ψ(e’)1 = (1/√6)(2Ψ1 – Ψ2 – Ψ3)

Ψ(e’)2 = (1/√2)(Ψ2 – Ψ3)

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Molecular Orbital Theory – LGOs for BH3

nodal planes

e’

a1’

Molecular Orbital Theory

18
Molecular Orbital Theory – BH3

Empty anti-bonding MOs

Empty non-bonding MO

Three bonding MOs are filled,

accounting for the three B-H σ
bonds

Molecular Orbital Theory

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 Molecular Orbital Theory – NH3

The ammonia molecule,

NH3, has C3v symmetry, with
a C3 principal axis of
symmetry and 3 vertical
planes of symmetry
z

N y
H
H
H x

Molecular Orbital Theory – NH3

Part of the character table of C3v

C3v E 2C3 3σv

A1 1 1 1

A2 1 1 -1

E 2 -1 0

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 Molecular Orbital Theory – NH3

Part of the character table of C3v

C3v E 2C3 3σv

2s and 2pz
A1 1 1 1 orbitals on N

A2 1 1 -1

E 2 -1 0

Molecular Orbital Theory – NH3

Part of the character table of C3v

C3v E 2C3 3σv

A1 1 1 1

A2 1 1 -1
2px and 2py
E 2 -1 0 orbitals on N

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 Molecular Orbital Theory – NH3

Part of the character table of C3v

C3v E 2C3 3σv

A1 1 1 1

A2 1 1 -1

E 2 -1 0
a1 + e
LGOs 3 0 1

2) Molecular Orbitals of NH3 (C3v)

• NH3 (C3v: E, 2C3, 3σv)

z
N 3H
NH3 2e -13.5 eV
H(3) H(1)
H(2)
y 4a1 - s2 + s3
e
x
-15.5 eV

The symmetry of 3H’s group orbitals: e (2px, 2py) a1 2s1 - s2 - s3

Γr = 3E+0C3+σv = A1 + E
a1 (2pz) 3a1 s1 + s2 + s3

C3v E 2C3 3σv -17.0 eV symmetry adapted

linear
A1 1 1 1 z x2+y2, z2 1e combinations
(SALC) of three 1s
a1 (2s) orbitals can be
A2 1 1 -1 found with help of
-25.6 eV the "projection
E 2 -1 0 (x,y) operator"
technique (F.A.
-31.0 eV Cotton, p. 114)
2a1

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 Molecular Orbital Theory

Molecular Orbital Theory – NH3

lone pair on N

N-H
bonding
orbitals

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 Molecular Orbital Theory – Methane Td

C3

Methane has Td
symmetry, a cubic point
group
The C3 axes in CH4
coincide with the C-H z
bonds
The C2 and S4 axes
coincide with the x, y,
and z axes y
x

Molecular Orbital Theory – Td character table

Part of the Td Character Table

Td E 8C3 3C2 6S4 6sd

A1 1 1 1 1 1
A2 1 1 1 -1 -1

E 2 -1 2 0 0

T1 3 0 -1 1 -1

T2 3 0 -1 -1 1

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Molecular Orbital Theory – Td character table

Part of the Td Character Table

Td E 8C3 3C2 6S4 6sd

A1 1 1 1 1 1 2s of C

A2 1 1 1 -1 -1
E 2 -1 2 0 0
T1 3 0 -1 1 -1
T2 3 0 -1 -1 1

Molecular Orbital Theory – Td character table

Part of the Td Character Table

Td E 8C3 3C2 6S4 6sd

A1 1 1 1 1 1
A2 1 1 1 -1 -1
E 2 -1 2 0 0
T1 3 0 -1 1 -1
2px, 2py, and
T2 3 0 -1 -1 1 2pz are triply
degenerate

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 Molecular Orbital Theory – Td character table

Part of the Td Character Table

Td E 8C3 3C2 6S4 6sd

A1 1 1 1 1 1
A2 1 1 1 -1 -1
E 2 -1 2 0 0
T1 3 0 -1 1 -1
T2 3 0 -1 -1 1
LGO 4 1 0 0 2 = a 1 + t2
s

Molecular Orbital Theory – Td character table

Wavefunctions for the LGOs for methane hydrogens

ψ(a1) = ½ (ψ1 + ψ2 + ψ3 + ψ4)

ψ(t2)1 = ½ (ψ1 - ψ2 + ψ3 - ψ4)

ψ(t2)2 = ½ (ψ1 + ψ2 - ψ3 - ψ4)

ψ(t2)3 = ½ (ψ1 - ψ2 - ψ3 + ψ4)

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Molecular Orbital Theory – LGOs for methane
C atomic orbitals

H ligand group orbitals

Molecular Orbital Theory - methane

27
 Molecular Orbital Theory – LGOs for F atoms
What if the atoms attached to the central atom are not H, and have
valence p orbitals, such as fluorines?

2) Molecular Orbitals of NH3 (C3v)

• NH3 (C3v: E, 2C3, 3σv)

z
N 3H
NH3 2e -13.5 eV
H(3) H(1)
H(2)
y 4a1 - s2 + s3
e
x
-15.5 eV

The symmetry of 3H’s group orbitals: e (2px, 2py) a1 2s1 - s2 - s3

Γr = 3E+0C3+σv = A1 + E
a1 (2pz) 3a1 s1 + s2 + s3

C3v E 2C3 3σv -17.0 eV symmetry adapted

linear
A1 1 1 1 z x2+y2, z2 1e combinations
(SALC) of three 1s
a1 (2s) orbitals can be
A2 1 1 -1 found with help of
-25.6 eV the "projection
E 2 -1 0 (x,y) operator"
technique (F.A.
-31.0 eV Cotton, p. 114)
2a1

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 3) Molecular Orbitals of CH4 (Td)
4H

The symmetry of 4H’s group orbitals: C

t2
Γr = 4E+1C3+0C2+0S4+2σd = A1 + T2
2t2
-13.5 eV s1+s2-s3-s4
z
3a1
t2
H(2) t2
H(1) -11.7 eV a1
y
C
x s1-s2+s3-s4
H(4)
H(3)
t2 (2px, 2py, 2pz) -14.8 eV t2
(-14, PhES)
Td 1t2
A1 x2+y2+z2 s1-s2-s3+s4
-22.3 eV
A2
E a1
a1 (2s)
T1
-25.7 eV
T2 (x,y,z) (-23, PhES)
2a1 s1+s2+s3+s4

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