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

py

dz2

Examples of atomic orbitals symmetry analysis

Atomic orbital C2v s px py pz dz2 dx2-y2 dxy dxz dyz
D4h A1g B1g B2g Eg A2u Eu (Rx,Ry) z (x, y) x2+y2, z2 x2-y2 xy (xz, yz)

Mulliken labels D3h D4h Td Oh

C2v A1 A2 B1 B2 D3h A1 A2 E A1 A2 E Oh x2+y2+z2 A1g Eg (2z2-x2-y2, x2-y2) T1g T2g (xz, yz, xy) T1u (x,y,z) (Rx,Ry,Rz) (xz, yz, xy) x2+y2+z2 (2z2-x2-y2, x2-y2) z (Rx,Ry) (xz, yz) Rz (x,y) (x2-y2, xy) x2+y2, z2 z Rz x, Ry y, Rx x2, y2, z2 xy xz yz

a1 b1 b2 a1 a1 a1 a2 b1 b2

a 1' e' e' a 2" a 1' e' e' e" e"

Td A1 A2 E T1 T2

a1g eu eu a2u a1g

a1 t2 t2 t2 e e t2 t2 t2

a1g t1u t1u t1u eg eg t2g t2g

b1g b2g eg eg

t2g

(Rx,Ry,Rz) (x,y,z)

MO diagram of homonuclear diatomic molecules

Filling the resulting MOs of homonuclear diatomic molecules with electrons leads to the following results:

6u 2g

AB

# of es

Bond order 1 0 1 2 3 2 1 0

# unpair. es 0 0 2 0 0 2 0 0

Bond energy, eV 1.1 3.0 6.4 9.9 5.2 1.4 -

2p

5g 1u

2p

Li2 Be2 B2 C2 N2 O2 F2 Ne2

6 8 10 12 14 16 18 20

2s

4u 3g 2u

2s

1s 1g

1s

Bond order = (#Bonding es - #Antibonding es)

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 - level inversion in this molecule. It also allows identify bonding (peaks with fine vibronic structure) and non-bonding MO (simple peaks) in it.
N 6 u 2 g 15.6 16.7 18.8 2s 3 g E, eV 1s 1 g 2 u 1s 2p 5 g 1 u 4u 2s 2p N

Lets Play with some MOs

waterwaterwater.

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

O H H
y

O (py)

B2

Oxygen

O (px)

B1

O (pz) A1 O (s)

O H H
y

Ha - Hb (s)

Hydrogen B1

Ha + Hb (s)

A1

NOW Lets Make Some MOs

LGOs B1

A1

A1

Oxygen

Hydrogens

NOW Lets Make Some MOs

LGOs B2 4 A1

A1

3 A1

A1 2 A1 Oxygen Hydrogens

NOW Lets Make Some MOs

LGOs B2 4 A1

A1

3 A1

A1 2 A1 Oxygen Hydrogens

NOW Lets Make Some MOs

2 B1 B1 LGOs

A1 1B2

1B1 A1

Oxygen

Hydrogens

NOW Lets Make Some MOs

2 B1 B1 LGOs

A1 1B2

1B1 A1

Oxygen

Hydrogens

NOW Lets Make Some MOs

2 B1 B1 4 A1 LGOs

A1 1B2 3 A1 1B1 A1 2 A1 Oxygen Hydrogens

NOW Lets Make Some MOs

2 B1 B1 4 A1 LGOs

A1 1B2 3 A1 1B1 A1 2 A1 Oxygen Hydrogens

Now for the Million Dollar Question

Why is Water Bent???

Molecular Orbital Theory linear XH2 molecules

Molecular Orbitals of BeH2

BeH2 (Dh)
H
y

Be
z

2H
5u
4g
s-s -13.5 eV

Be

u+

Group orbitals of 2H's:

2px
s - s

u
2py

2.2 eV

u
2pz

s+s

u+

g+

g+
s + s

2s -8.2 eV

3u

1g22g23u2
Dh g+ u+ u v 1 1 0 i 1 -1 -2 z (x,y) x2+y2, z2
1s

2g

-128 eV

1g

10

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 X H
Water 104.5

O H H

11

4) MO theory and molecular geometry (Walsh diagrams) Correlate changes in energy of MOs between species ABx of high and lower symmetry, such as BeH2 and H2O.
z

5u
O H
y

2b2 4a1 4g

b1 3a1

BeH2 BH2 CH2 NH2 OH2 FH2+

2g23u2 linear 2a121b223a11 , 131o 2a121b223a12 , 102o 2a121b223a121b11 , 103o 2a121b223a121b12 , 105o 2a121b223a121b12 , 113o

3u

1b2

2g

2a1

Molecular Orbital Theory BH3

BH3 has a C3 principal axis of symmetry, 3 C2 axes ( C3), 3 v, and h it is in a D3h point group

12

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

H B H x H

Molecular Orbital Theory D3h Character Table

D3h A1 A2 E A1 A2 E

E 1 1 2 1 1 2

2C3 1 1 -1 1 1 -1

3C2 1 -1 0 1 -1 0

h 1 1 2 -1 -1 -2

2S3 1 1 -1 -1 -1 1

3v 1 -1 0 -1 1 0

13

Molecular Orbital Theory D3h Character Table

D3h E A1 A2 E A1 A2 E 1 1 2 1 1 2

2C3 3C2 h 1 1 -1 1 1 -1 1 -1 0 1 -1 0 1 1 2 -1 -1 -2

2S3 3v 1 1 -1 -1 -1 1 1 -1 0 -1 1 0

Molecular Orbital Theory D3h Character Table

D3h E A1 A2 E A1 A2 E 1 1 2 1 1 2

2C3 3C2 h 1 1 -1 1 1 -1 1 -1 0 1 -1 0 1 1 2 -1 -1 -2

2S3 3v 1 1 -1 -1 -1 1 1 -1 0 -1 1 0 2s

14

Molecular Orbital Theory D3h Character Table

D3h E A1 A2 E A1 A2 E 1 1 2 1 1 2

2C3 3C2 h 1 1 -1 1 1 -1 1 -1 0 1 -1 0 1 1 2 -1 -1 -2

2S3 3v 1 1 -1 -1 -1 1 1 -1 0 -1 1 0
2pz

Molecular Orbital Theory D3h Character Table

D3h E A1 A2 E A1 A2 E 1 1 2 1 1 2

2C3 3C2 h 1 1 -1 1 1 -1 1 -1 0 1 -1 0 1 1 2 -1 -1 -2

2S3 3v 1 1 -1 -1 -1 1 1 -1 0 -1 1 2px 0 2py doubly degenerate

15

Molecular Orbital Theory D3h Character Table

D3h E A1 A2 E A1 A2 E 1 1 2 1 1 2

2C3 3C2 h 1 1 -1 1 1 -1 1 -1 0 1 -1 0 1 1 2 -1 -1 -2

2S3 3v 1 1 -1 -1 -1 1 1 -1 0 -1 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 3

C3 0

C2 1

h 3

S3 0

v 1

16

Molecular Orbital Theory LGOs on H atoms

E 3 C3 0 C2 1 h 3 S3 0 v 1

The resulting row of characters is also obtained by adding the characters of the A1 and E representations

D3h A1 E

E 1 2

2C 3C h
3 2

2S 3
3 v

1 -1 0

1 0 1

1 2 3

1 -1 0

1 0 1

LGOs 3

Molecular Orbital Theory LGOs for BH3

(a1) = (1/3)(1 + 2 + 3) (e)1 = (1/6)(21 2 3) (e)2 = (1/2)(2 3)

17

Molecular Orbital Theory LGOs for BH3

nodal planes

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 bonds

Molecular Orbital Theory

19

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 H

H H x

Molecular Orbital Theory NH3

Part of the character table of C3v

C3v A1 A2 E

E 1 1 2

2C3 1 1 -1

3v 1 -1 0

20

Molecular Orbital Theory NH3

Part of the character table of C3v

C3v A1 A2 E

E 1 1 2

2C3 1 1 -1

3v 1 -1 0
2s and 2pz orbitals on N

Molecular Orbital Theory NH3

Part of the character table of C3v

C3v A1 A2 E

E 1 1 2

2C3 1 1 -1

3v 1 -1 0
2px and 2py orbitals on N

21

Molecular Orbital Theory NH3

Part of the character table of C3v

C3v A1 A2 E LGOs

E 1 1 2 3

2C3 1 1 -1 0

3v 1 -1 0 1
a1 + e

2) Molecular Orbitals of NH3 (C3v) NH3 (C3v: E, 2C3, 3v)

z

N
2e

3H
-13.5 eV

NH3 H(3) H(1) H(2)

y x
-15.5 eV e (2px, 2py)

4a1

- s2 + s3

The symmetry of 3Hs group orbitals: r = 3E+0C3+v = A1 + E

a1

2s1 - s2 - s3

a1 (2pz)

3a1
-17.0 eV

s1 + s2 + s3
symmetry adapted linear combinations (SALC) of three 1s orbitals can be found with help of the "projection operator" technique (F.A. Cotton, p. 114)

C3v A1 A2 E

E 2C3 3v 1 1 1 1 2 -1 1 -1 0 (x,y)
-31.0 eV 2a1

x2+y2, z2
a1 (2s) -25.6 eV

1e

22

Molecular Orbital Theory

Molecular Orbital Theory NH3

lone pair on N

N-H bonding orbitals

23

Molecular Orbital Theory Methane Td

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

Molecular Orbital Theory Td character table

Part of the Td Character Table

Td A1 A2 E T1 T2

E 1 1 2 3 3

8C3 3C2 6S4 6sd 1 1 -1 0 0 1 1 2 -1 -1 1 -1 0 1 -1 1 -1 0 -1 1

24

Molecular Orbital Theory Td character table

Part of the Td Character Table

Td A1 A2 E T1 T2

E 1 1 2 3 3

8C3 1 1 -1 0 0

3C2 1 1 2 -1 -1

6S4 1 -1 0 1 -1

6sd 1 -1 0 -1 1
2s of C

Molecular Orbital Theory Td character table

Part of the Td Character Table

Td A1 A2 E T1 T2

E 1 1 2 3 3

8C3 1 1 -1 0 0

3C2 1 1 2 -1 -1

6S4 1 -1 0 1 -1

6sd 1 -1 0 -1 1
2px, 2py, and 2pz are triply degenerate

25

Molecular Orbital Theory Td character table

Part of the Td Character Table

Td A1 A2 E T1 T2 LGO s

E 1 1 2 3 3 4

8C3 1 1 -1 0 0 1

3C2 1 1 2 -1 -1 0

6S4 1 -1 0 1 -1 0

6sd 1 -1 0 -1 1 2
= a 1 + t2

Molecular Orbital Theory Td character table

Wavefunctions for the LGOs for methane hydrogens (a1) = (1 + 2 + 3 + 4) (t2)1 = (1 - 2 + 3 - 4) (t2)2 = (1 + 2 - 3 - 4) (t2)3 = (1 - 2 - 3 + 4)

26

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, 3v)

z

N
2e

3H
-13.5 eV

NH3 H(3) H(1) H(2)

y x
-15.5 eV e (2px, 2py) 4a1

- s2 + s3

The symmetry of 3Hs group orbitals: r = 3E+0C3+v = A1 + E

a1

2s1 - s2 - s3

a1 (2pz)

3a1
-17.0 eV

s1 + s2 + s3
symmetry adapted linear combinations (SALC) of three 1s orbitals can be found with help of the "projection operator" technique (F.A. Cotton, p. 114)

C3v A1 A2 E

E 2C3 3v 1 1 1 1 2 -1 1 -1 0 (x,y)
-31.0 eV 2a1

x2+y2, z2
a1 (2s) -25.6 eV

1e

28

3) Molecular Orbitals of CH4 (Td)

4H

The symmetry of 4Hs group orbitals: r = 4E+1C3+0C2+0S4+2d = A1 + T2

C
t2

2t2
-13.5 eV
z H(2) H(1) y x H(3) C H(4)

s1+s2-s3-s4 t2 s1-s2+s3-s4

3a1

t2 a1

-11.7 eV

t2 (2px, 2py, 2pz)

Td A1 A2 E T1 T2 (x,y,z) x2+y2+z2

-14.8 eV (-14, PhES) 1t2

t2 s1-s2-s3+s4 a1

-22.3 eV a1 (2s)
-25.7 eV (-23, PhES) 2a1

s1+s2+s3+s4

29