Computational Chemistry

O

H H

HH

Cs

C3v

103.7

104.1

103.0

103.9

(104.5)

C2v

B3LYP / 6-31G*

Experiment

0.969

0.964

0.976

0.969

(0.958) MP2(fc) / 6-31G*

M06 / 6-31G*

TPSS / 6-31G*

C

1.071

1.072

1.073

1.069

(1.065)

1.157

1.157

1.166

1.177

(1.153) Civ

HN C2v

H

H

H

H

H H

1.533

1.520

1.537

1.526

(1.526)

H H

112.8

112.0

112.7

112.3

(112.4)

O O

H

H

0.971

0.982

0.976

(0.965)

99.6

100.5

98.7

98.6

(100.0)

0.973 C^2 1.108 1.100

(1.099)

1.098

1.092

(1.099)

1.473

1.465

(1.471)

1.025

1.018

(1.010)

115.9

115.4

(113.9)

Cs

1.096

1.019

1.104

1.465

115.7

N

H

H

H

H H

1.097

1.106

115.9

1.454

1.017

H

H

H

H

H H

125.1

124.5

(124.3)

1.340

1.338

(1.318)

1.506

1.499

(1.501)

Cs

1.333 1.503

125.1

1.330

124.8

1.492

106.1

106.3

(107.2)

O

H

H

H

H

0.976

0.970

(0.963)

1.104

1.097

(1.094)

1.105

1.090

(1.094)

106.9

107.4

(108.0)

Cs

1.093

1.101

107.7

0.969

106.7

1.419

1.404

1.429

1.425

(1.421)

1.095

107.0

108.0

0.965 H C2v

H

H

H

H H

O

116.6

116.4

(117.2)

1.225

1.228

(1.222)

1.526

1.513

(1.507)

1.216 1.520

116.7

1.211 1.509

115.7

H

H

H

1.464 1.463 H

(1.459)

1.214

1.220

(1.206)

1.460

1.2071.206

1.453

O

H H

1.216

1.221

(1.208)

1.113

1.104

(1.116)

115.4

115.6

(116.5)

C2v

1.110

1.207

115.3

1.114

114.7

1.200

D3d

H

H

H

H

HH

1.535

1.526

(1.531)

1.099

1.093

107.7 107.7 (1.096)

(107.8)

107.5

1.096

1.531

107.4

1.097

1.519

H

H

H 1.8081.779

(1.781)

1.093

1.089

(1.096)

110.7

110.0

(110.0)

C3v

110.4 Cl

1.090

110.2 1.803

1.790

1.092

H Cs

101.5

102.6

(102.5)

0.984

0.979

(0.975)

1.743

1.717

O (1.690)

Cl

0.976 1.728

102.4

0.972

103.2

1.700

S

H H

1.350

1.340

(1.336)

92.6

93.3

(92.1)

92.9 C 2 v

1.3491.348

92.6

F

H

H

H

1.393

1.392

(1.383)

1.099

1.092

(1.100)

109.5

109.8

(110.6)

C3v

109.4

1.384

1.096

109.0

1.366

1.098 H

H

H

H

116.3 116.6 D2h

(117.8)

1.090

1.085

(1.085)

1.337

1.337

(1.339)

1.088

116.3

1.331

116.1

1.327

1.089

H

H

H

H 1.839 1.816

(1.819)

1.351

1.341

(1.336)

1.350

1.095

1.090

(1.091)

1.095

1.091

(1.091)

S

97.0

96.4

96.7

96.8

(96.5)

1.092

1.093 1.836

1.094

1.094

1.823

1.348

H

O

97.1 F

97.2

(96.8)

0.985

0.979

(0.966)

1.453

1.445

(1.442)

Cs

0.977 1.434

97.8

1.410

98.4

0.975

Dih

1.069

1.066

(1.061)

1.211

1.218

(1.203)

1.067

1.205

1.069

1.204 Me S O

Me

1.852

1.809

(1.799)

1.521

1.512

(1.485)

107.9

107.4

(106.7)

94.9

95.8

(96.6)

Cs

1.837 1.511

107.6

95.894.8

1.823 1.498

106.8

1.103

1.428

1.479

1.469

(1.452)

1.456

Fig. 7.1 A comparison of some B3LYP, M06, TPSS, MP2(fc), and experimental geometries. The
basis set is 6-31G*. Calculations are by the author and experimental geometries are from [ 69 ].
Note that all CH bonds are ca. 1 A ̊, and all other bonds range from ca. 1.2 to 1.8 A ̊, and all bond
angles (except for linear molecules) are ca. 90to 120

7.3 Applications of Density Functional Theory 469