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py
dz2
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
a1 t2 t2 t2 e e t2 t2 t2
b1g b2g eg eg
t2g
(Rx,Ry,Rz) (x,y,z)
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
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
A1
A1
Oxygen
Hydrogens
A1
3 A1
A1 2 A1 Oxygen Hydrogens
A1
3 A1
A1 2 A1 Oxygen Hydrogens
A1 1B2
1B1 A1
Oxygen
Hydrogens
A1 1B2
1B1 A1
Oxygen
Hydrogens
Be
z
2H
5u
4g
s-s -13.5 eV
Be
u+
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
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
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
17
a1
18
Empty non-bonding MO
Three bonding MOs are filled, accounting for the three B-H bonds
19
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
N
2e
3H
-13.5 eV
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
Td A1 A2 E T1 T2
E 1 1 2 3 3
24
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
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
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
27
N
2e
3H
-13.5 eV
- 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
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 s1-s2-s3+s4 a1
-22.3 eV a1 (2s)
-25.7 eV (-23, PhES) 2a1
s1+s2+s3+s4
29