58.8 (44.0, 30.2)

55.7

59.8 (64.6, 40.4)

58.1

54.9 (41.1, 26.9)

61.7 (69.9, 29.8)

53.4

62.8 (73.9, 34.9)

60.8

52.1 (69.8, 29.2)

76.2 (66.3, 42.6)

68.9

65.5 (89.6, 57.4)

75.1

67.1 (65.7, 43.7)

B3LYP/6-31+G**MPW1PW91/6-31+G**MP2/6-31+G**B3LYP/aug-cc-pVDZMPW1PW91/aug-cc-Pvdz

括弧內數字代表 S-T gap

130.5 (56.4, 5.7)

115.4

138.0 (31.1, 11.2)

128.6

112.1 (50.2, 13.1)

77.5 (57.8, 10.4)

70.4

75.2 (68.1, 20.2)

75.6

68.1 (63.9, 9.7)

B3LYP/6-31+G**MPW1PW91/6-31+G**MP2/6-31+G**B3LYP/aug-cc-pVDZMPW1PW91/aug-cc-pVDZ

括弧內數字代表 S-T gap

C6H → C2 + C4H C6H- → C2 + C4H-

B3LYPkcal/mol

kcal/mol

C6H C2 C4H 反應能 C6H- C2 C4H- 反應能

-228.952

69

-75.888

24

-152.783

95176.02

-229.085

21

-75.888

24

-152.909

47180.41

MP2

C6H C2 C4H C6H- C2 C4H-

-228.180

84

-75.701

18

-152.273

2129.56

-228.370

45

-75.701

18

-152.425

03153.26

0

20

40

60

80

100

120

140

160

180

1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8

bond length(A)

rel e

nerg

y(kc

al/m

ol)

MP2

B3LYP

C6H → C2 + C4H

S

T

R(1,5)

R(1,2)

R(2,6)A(5,1,

2)A(1,2,

6)A(2,3,

7)

1.274

1.454

1.329179.2

879.7

179.84

1.281.48

31.325 155.4 69.29

179.87

1.283

1.48 1.328153.0

168.47

9179.8

7

R(1,5)

R(1,2) R(2,6)A(5,1,2

)

A(1,2,6)

A(2,3,7)

1.42 1.377 1.386 150.11 64.63179.6

1

1.395 1.414 1.405 148.98 62.21178.1

6

1.401 1.407 1.406 148.82 62.34177.9

4

MP2/6-31+G**B3LYP/6-31+G**MPW1PW91/aug-cc-pVDZ

S

T

R(1,4)R(1,5

)R(1,2)

A(4,1,5)

A(4,1,2

A(3,2,6)

1.427 1.427 1.355 59.29150.2

457.94

1.426 1.426 1.355 58.65150.6

357.04

1.424 1.424 1.355 59.01150.4

457.38

R(1,4) R(1,5) R(1,2) A(4,1,5)A(4,1,

2)A(3,2,

6)

1.437 1.449 1.359 56.27 153.1 56.92

1.437 1.469 1.356 55.22 154.5 56.58

1.434 1.468 1.357 55.43 154.6 56.92

MP2/6-31+G**B3LYP/6-31+G**MPW1PW91/aug-cc-pVDZ

S

T

R(1,2)R(1,7

)R(6,7)

A(1,7,6)

A(7,1,2)

A(1,2,4)

1.516 1.415 1.414 65.14 117.26 121.53

1.521 1.407 1.407 64.5 118.11 122.54

1.515 1.41 1.41 64.22 118.19 122.36

R(1,2) R(1,7) R(6,7) A(1,7,6)A(7,1,

2)A(1,2,4

)

1.558 1.356 1.356 77.99 103.3 123.05

1.572 1.372 1.372 79.44 101.6 122.13

1.562 1.372 1.372 78.71 101.9 121.62

MP2/6-31+G**B3LYP/6-31+G**MPW1PW91/aug-cc-pVDZ

S

T

R(1,2)

R(1,6)

R(4,5)R(2,7

)

A(4,1,6)

A(6,1,2)

A(3,2,7)

1.551.48

81.535 1.34 61.12

124.34

142.53

1.5341.39

71.388 1.45 62.65 72.38 131.26

1.5331.40

61.399 1.46 61.81 69.52 131.56

R(1,2)

R(1,6)

R(4,5)R(2,

7)

A(4,1,6)

A(6,1,2)

A(3,2,7)

1.421.47

11.41

1.379

90.54 133.67 122.71

1.423

1.478

1.4111.38

190.21 133.31 121.5

1.421.47

81.412

1.381

90.25 133.47 121.68

MP2/6-31+G**B3LYP/6-31+G**MPW1PW91/aug-cc-pVDZ

S

T

R(1,3)

R(3,5)

R(1,2)A(3,1,

2)A(3,5,

4)A(1,2,

6)

1.448 1.46 1.413133.5

488.57

7177.3

3

1.4521.45

71.407

133.88

89.35177.4

5

1.448 1.46 1.407134.2

388.72

177.35

R(1,3) R(3,5) R(1,2)A(3,1,2

)

A(3,5,4)

A(1,2,6)

1.429 1.462 1.4 139.65 71.38 177.63

1.441 1.456 1.37 143.08 71.94 176.17

1.439 1.456 1.369 143.5 71.5 174.69

MP2/6-31+G**B3LYP/6-31+G**MPW1PW91/aug-cc-pVDZ