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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

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)

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

Td A1 A2 E T1 T2

a1 t2 t2 t2 e e t2 t2 t2

b1g b2g eg eg

t2g

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

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

2p

5g 1u

2p

6 8 10 12 14 16 18 20

2s

4u 3g 2u

2s

1s 1g

1s

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

waterwaterwater.

You use some Acronyms! Sounds Good! SALCs Symmetry Adapted Linear Combinations LGOs Ligand Group Orbitals

Oxygen

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

LGOs B1

A1

A1

Oxygen

Hydrogens

LGOs B2 4 A1

A1

3 A1

A1 2 A1 Oxygen Hydrogens

LGOs B2 4 A1

A1

3 A1

A1 2 A1 Oxygen Hydrogens

2 B1 B1 LGOs

A1 1B2

1B1 A1

Oxygen

Hydrogens

2 B1 B1 LGOs

A1 1B2

1B1 A1

Oxygen

Hydrogens

2 B1 B1 4 A1 LGOs

2 B1 B1 4 A1 LGOs

Why is Water Bent???

BeH2 (Dh)

H

y

Be

z

2H

5u

4g

s-s -13.5 eV

Be

u+

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

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

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

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

3u

1b2

2g

2a1

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

12

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

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

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

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

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

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

15

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

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

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

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

17

nodal planes

a1

18

Empty anti-bonding MOs

Empty non-bonding MO

Three bonding MOs are filled, accounting for the three B-H bonds

19

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

C3v A1 A2 E

E 1 1 2

2C3 1 1 -1

3v 1 -1 0

20

C3v A1 A2 E

E 1 1 2

2C3 1 1 -1

3v 1 -1 0

2s and 2pz orbitals on N

C3v A1 A2 E

E 1 1 2

2C3 1 1 -1

3v 1 -1 0

2px and 2py orbitals on N

21

C3v A1 A2 E LGOs

E 1 1 2 3

2C3 1 1 -1 0

3v 1 -1 0 1

a1 + e

z

N

2e

3H

-13.5 eV

y x

-15.5 eV e (2px, 2py)

4a1

- s2 + s3

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

lone pair on N

23

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

Part of the Td Character Table

Td A1 A2 E T1 T2

E 1 1 2 3 3

24

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

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

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

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

C atomic orbitals

27

What if the atoms attached to the central atom are not H, and have valence p orbitals, such as fluorines?

z

N

2e

3H

-13.5 eV

y x

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

- s2 + s3

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

4H

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

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

t2 s1-s2-s3+s4 a1

-22.3 eV a1 (2s)

-25.7 eV (-23, PhES) 2a1

s1+s2+s3+s4

29

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