Benzyl Alcohol

2012/07/17

Geometries at the B3LYP/aug-cc-pVTZ level

　 　 dHOCC dOCC5C rOH relative energy (kcal/mol)

including ZPE

1 gauche cis 54.8 55.4 0.963 0.0 0.0 2 173.9 -18.8 0.961 1.0 0.8 3 -176.5 10.7 0.960 1.0 0.8 4 planar 180.0 0.0 0.960 1.0 0.8

1 (gauche cis) 2

3 4 (planar)(Cs symmetry)

2

3Dissociation pathways in the ground state at the G3(MP2, CCSD) and CCSD(T)/ptz (including B3LYP/aptz ZPE) in the

parentheses

0

20

40

60

80

100

120

84.4(83.6) 88.8(85.8)

15.2(14.7)

102.9(101.4)

0.0(0.0)

81.6(80.6)

98.4(99.3)

75.2(76.7) 71.4(70.0)

76.5(77.5)

rela

tive

ener

gy (k

cal/m

ol)

C6H5CH2OH

C6H5CH2O + H

C6H5CHOH + H

C6H5CH2 + OH

C6H5 + CH2OH

C6H6 + CH2O TS

C6H6 + CH2O

C6H5CH + H2O TS

C6H5CH + H2O complex

C6H5CH(S) + H2O

C6H5CH (triplet state is 3.2 kcal/mol lower than singlet state at CCSD(T)/ptz level)

4Calculated reaction energetics (kcal/mol, including ZPE) in the ground electronic state

pathway 1: benzyl alcohol → C6H5CH2O + H

　 reaction energyB3LYP/6-31G 90.2

B3LYP/6-311+G** 119.0 B3LYP/aug-cc-pVTZ 97.8

M06-2X/6-311+G** SP 101.2 MP2/aptz SP 108.0

CCSD(T)/ptz SP 101.4 MLSE(C1)-M06-2X 104.4

paper_G3(MP2,CCSD) 102.9

pathway 2: benzyl alcohol → C6H5CHOH + H

　 reaction energyB3LYP/6-31G 79.3

B3LYP/6-311+G** 100.3 B3LYP/aug-cc-pVTZ 77.9

M06-2X/6-311+G** SP 82.1 MP2/aptz SP 106.0

CCSD(T)/ptz SP 83.6 MLSE(C1)-M06-2X 84.8

paper_G3(MP2,CCSD) 84.4

pathway 3: benzyl alcohol → C6H5CH2 + OH

　 reaction energyB3LYP/6-31G 69.2

B3LYP/6-311+G** 94.7 B3LYP/aug-cc-pVTZ 73.0

M06-2X/6-311+G** SP 82.1 MP2/aptz SP 110.8

CCSD(T)/ptz SP 80.6 MLSE(C1)-M06-2X 83.4

paper_G3(MP2,CCSD) 81.6

pathway 4: benzyl alcohol → C6H5 + CH2OH

　 reaction energyB3LYP/6-31G 93.7

B3LYP/6-311+G** 111.1 B3LYP/aug-cc-pVTZ 88.7

M06-2X/6-311+G** SP 97.4 MP2/aptz SP 128.1

CCSD(T)/ptz SP 99.3 MLSE(C1)-M06-2X 101.1

paper_G3(MP2,CCSD) 98.4

5Calculated reaction energetics (kcal/mol, including ZPE) in the ground electronic state

pathway 5: benzyl alcohol → C6H6 + CH2O　 barrier reaction energyB3LYP/6-31G 83.2 12.0

B3LYP/6-311+G** 103.5 32.3 B3LYP/aug-cc-pVTZ 81.1 10.5

M06-2X/6-311+G** SP 85.5 17.6 MP2/aptz SP 83.2 18.2

CCSD(T)/ptz SP 85.8 14.7 MLSE(C1)-M06-2X 83.7 16.8

paper_G3(MP2,CCSD) 88.8 15.2

pathway 6: benzyl alcohol → C6H5CH(singlet, triplet) + H2O　 barrier complex reaction energy　 　 　 C6H5CH(S) + H2O C6H5CH(T) + H2O

B3LYP/6-31G 71.8 70.8 85.6 74.5 B3LYP/6-311+G** 92.1 86.2 94.4 88.9

B3LYP/aug-cc-pVTZ 70.5 65.2 72.5 66.8 M06-2X/6-311+G** SP 80.7 71.2 80.1 72.6

MP2/aptz SP 79.1 73.0 81.4 99.1 CCSD(T)/ptz SP 76.7 70.0 77.5 74.3

MLSE(C1)-M06-2X 75.3 69.0 76.7 74.7 paper_G3(MP2,CCSD) 75.2 71.4 76.5 　

C6H5CH (triplet state is 3.2 kcal/mol lower than singlet state at CCSD(T)/ptz level)

6Possible excited states of dissociation productsphoto energy: 147.8 kcal/mol

pathway 1: benzyl alcohol → C6H5CH2O + H reaction energy: 101.4 kcal/mol

以 doublet state C6H5CH2O 結構計算 TD-B3LYP/6-311+G**

C6H5CH2Oground state

A"Excited state 1

A"Excited state 2

A'Excited state 3

A'eV 　 0.47 2.05 2.28

kcal/mol 0.00 10.76 47.26 52.49 pathway 2: benzyl alcohol → C6H5CHOH + H reaction energy: 83.6 kcal/mol

以 doublet state C6H5CHOH 結構計算 TD-B3LYP/6-311+G**

C6H5CHOH ground stateA"

Excited state 1 A'

Excited state 2 A'

Excited state 3 A"

eV 　 2.84 3.35 3.40 kcal/mol 0.00 65.59 77.23 78.34

pathway 3: benzyl alcohol → C6H5CH2 + OH reaction energy: 80.6 kcal/mol

以 doublet state C6H5CH2 結構計算 TD-B3LYP/6-311+G**

C6H5CH2ground state

B1Excited state 1

B2Excited state 2

A1eV 　 3.17 3.39

kcal/mol 0.00 73.08 78.23

7Possible excited states of dissociation productsphoto energy: 147.8 kcal/mol

pathway 6: benzyl alcohol → C6H5CH + H2O reaction energy: 77.5(S), 74.3(T) kcal/mol以 triplet state C6H5CH 結構計算 TD-B3LYP/6-311+G**

C6H5CH Triplet ground state-A"

Excited state 1 A'

Excited state 2 A'

eV 　 3.28 3.53 kcal/mol 0.00 75.70 81.48

以 singlet state C6H5CH 結構計算 TD-B3LYP/6-311+G**

C6H5CH Triplet ground state-A"

Singlet ground state-A'

Excited state 1 Singlet-A"

Excited state 2 Triplet-A'

Excited state 3 Triplet-A'

Excited state 4 Triplet-A"

eV -0.72 　 1.16 2.97 3.09 3.68 kcal/mol -16.49 0.00 26.67 68.37 71.27 84.89

8Dissociation pathways in the triplet state at the G3(MP2, CCSD) and CCSD(T)/ptz (including B3LYP/aptz ZPE) in the

parentheses

70

80

90

100

110

120

130

84.4(83.6)

98.6(100.2)

79.5(78.7)

(74.3)

98.4(99.3)

118.3(112.2)

104.7

85.3(96.9)

114.1

102.9(101.4)

81.6(80.6)rela

tive

ener

gy (k

cal/m

ol)

C6H5CH2OH

C6H5 + CH2OH

C6H5 + CH2OH TS

C6H5CHOH + H

C6H5CHOH + H TS C6H5CH2O + H

conical intersection

C6H5CH2 + OH

C6H5CH2 + OH complex

C6H5CH2 + OH TS

C6H5CH(T) + H2O

9Calculated reaction energetics (kcal/mol, relative to the singlet ground state) in the triplet electronic state

benzyl alcohol(singlet) → benzyl alcohol(triplet)　 S-T gap

B3LYP/6-31G 82.5 B3LYP/6-311+G** 101.7

B3LYP/aug-cc-pVTZ 80.4 M06-2X/6-311+G** SP 86.3

MP2/aptz SP 106.5 MP2/ptz SP 106.8

CCSD(T)/ptz SP 96.9 MLSE(C1)-M06-2X 85.9

paper_G3(MP2,CCSD) 85.3

pathway 1: benzyl alcohol → C6H5 + CH2OH

　 barrier reaction energyB3LYP/6-31G 107.7 93.7

B3LYP/6-311+G** 125.8 111.1 B3LYP/aug-cc-pVTZ 104.1 88.7

M06-2X/6-311+G** SP 110.5 97.4 MP2/aptz SP 139.6 128.1

CCSD(T)/ptz SP 112.2 99.3 MLSE(C1)-M06-2X 113.1 101.1

paper_G3(MP2,CCSD) 118.3 98.4

pathway 2: benzyl alcohol → C6H5CHOH + H

　 barrier reaction energyB3LYP/6-31G 79.3

B3LYP/6-311+G** 100.3 B3LYP/aug-cc-pVTZ 77.9

M06-2X/6-311+G** SP 82.1 MP2/aptz SP 106.0

CCSD(T)/ptz SP 83.6 MLSE(C1)-M06-2X 84.8

paper_G3(MP2,CCSD) 104.7 84.4

10Calculated reaction energetics (kcal/mol, relative to the singlet ground state) in the triplet electronic state

pathway 3: benzyl alcohol → C6H5CH2O + H

　 barrier reaction energyB3LYP/6-31G 90.2

B3LYP/6-311+G** 119.0 B3LYP/aug-cc-pVTZ 97.8

M06-2X/6-311+G** SP 101.2 MP2/aptz SP 108.0

CCSD(T)/ptz SP 101.4 MLSE(C1)-M06-2X 104.4

paper_G3(MP2,CCSD) 114.1 102.9

pathway 4: benzyl alcohol → C6H5CH2 + OH

　 barrier complex reaction energyB3LYP/6-31G 89.0 66.7 69.2

B3LYP/6-311+G** 112.6 93.2 94.7 B3LYP/aug-cc-pVTZ 91.2 71.9 73.0

M06-2X/6-311+G** SP 103.1 79.7 82.1 MP2/aptz SP 127.3 108.8 110.8

CCSD(T)/ptz SP 100.2 78.7 80.6 MLSE(C1)-M06-2X 99.9 81.6 83.4

paper_G3(MP2,CCSD) 98.6 79.5 81.6

11The energies (kcal/mol) along the O-H bond distance in hydroxyl group of the planar conformation

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 0.0

50.0

100.0

150.0

200.0

250.0

300.0 1A'

2A'

1A"

2A"

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol)

CASSCF/6-31+G**

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 0.0

50.0

100.0

150.0

200.0

250.0 1A'

2A'

1A"

2A"

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol)

TD-B3LYP/6-311+G**

12The energies (kcal/mol) along the O-H bond distance in hydroxyl group of the gauche cis conformation

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 0.0

50.0

100.0

150.0

200.0

250.0 1A2A3A4A

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol)

TD-B3LYP/6-311+G**

0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 0.0

50.0

100.0

150.0

200.0

250.0

300.0 1A2A3A4A

O-H bond distance (Å)O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol)

CASSCF/6-31+G**