Benzyl Alcohol

Benzyl Alcohol

2012/07/11

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

3

Dissociation pathways in the ground electronic state at the MLSE(C1)-M06-2X

0

20

40

60

80

100

120

93.2195331931241

89.1000816086168

20.6536373550795

114.015402550429

0.0

89.7722058988697

106.620751347105

80.9844167775467 72.922896482840

5

82.7671403603482

rela

tive

ener

gy (k

cal/m

ol)

C6H5CH2OH

C6H5CH2O + H

C6H5CHOH + H

C6H5CH2 + OH

C6H5 + CH2OH

C6H6 + CH2O TS

C6H6 + CH2O

C6H5CH + H2O TSC6H5CH + H2O complex

C6H5CH + H2O

4

Calculated reaction energetics (kcal/mol) in the ground electronic state

pathway 1: benzyl alcohol → C6H5CH2O + H

　 reaction energyB3LYP/6-31G 99.8

B3LYP/6-311+G** 128.6 M06-2X/6-311+G** SP 110.8

MP2/aptz SP 117.5 MLSE(C1)-M06-2X 114.0

paper_G3(MP2,CCSD) 102.9

pathway 2: benzyl alcohol → C6H5CHOH + H

　 reaction energyB3LYP/6-31G 87.7

B3LYP/6-311+G** 108.7 M06-2X/6-311+G** SP 90.5

MP2/aptz SP 114.4 MLSE(C1)-M06-2X 93.2

paper_G3(MP2,CCSD) 84.4

pathway 3: benzyl alcohol → C6H5CH2 + OH

　 reaction energyB3LYP/6-31G 75.6

B3LYP/6-311+G** 101.1 M06-2X/6-311+G** SP 88.5

MP2/aptz SP 117.2 MLSE(C1)-M06-2X 89.8

paper_G3(MP2,CCSD) 81.6

pathway 4: benzyl alcohol → C6H5 + CH2OH

　 reaction energyB3LYP/6-31G 99.2

B3LYP/6-311+G** 116.6 M06-2X/6-311+G** SP 103.0

MP2/aptz SP 133.6 MLSE(C1)-M06-2X 106.6

paper_G3(MP2,CCSD) 98.4

5

pathway 5: benzyl alcohol → C6H6 + CH2O　 barrier reaction energyB3LYP/6-31G 88.7 15.9

B3LYP/6-311+G** 108.9 36.2 M06-2X/6-311+G** SP 90.9 21.4

MP2/aptz SP 88.6 22.1 MLSE(C1)-M06-2X 89.1 20.7

paper_G3(MP2,CCSD) 88.8 15.2

pathway 6: benzyl alcohol → C6H5CH + H2O　 barrier complex reaction energyB3LYP/6-31G 77.5 74.7 91.6

B3LYP/6-311+G** 97.7 90.2 100.5 M06-2X/6-311+G** SP 86.4 75.1 86.1

MP2/aptz SP 84.7 77.0 87.5 MLSE(C1)-M06-2X 81.0 72.9 82.8

paper_G3(MP2,CCSD) 75.2 71.4 76.5

Calculated reaction energetics (kcal/mol) in the ground electronic state

6

Dissociation pathways in the triplet electronic state at the MLSE(C1)-M06-2X

80

90

100

110

120

130

140

93.2

104.7

86.9

106.6

117.5

90.3

114.0

89.8

rela

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ener

gy (k

cal/m

ol)

C6H5CH2OH

C6H5 + CH2OH

C6H5 + CH2OH TS

C6H5CHOH + H

C6H5CHOH + H TS

C6H5CH2O + H

C6H5CH2O + H TS

C6H5CH2 + OH

C6H5CH2 + OH complex

C6H5CH2 + OH TS

7

Calculated reaction energetics (kcal/mol) in the triplet electronic state

pathway 1: benzyl alcohol → C6H5 + CH2OH

　 barrier reaction energyB3LYP/6-31G 112.1 99.2

B3LYP/6-311+G** 130.2 116.6 M06-2X/6-311+G** SP 114.9 103.0

MP2/aptz SP 144.0 133.6 MLSE(C1)-M06-2X 117.5 106.6

paper_G3(MP2,CCSD) 118.3 98.4

pathway 2: benzyl alcohol → C6H5CHOH + H

　 barrier reaction energyB3LYP/6-31G 87.7

B3LYP/6-311+G** 108.7 M06-2X/6-311+G** SP 90.5

MP2/aptz SP 114.4 MLSE(C1)-M06-2X 93.2

paper_G3(MP2,CCSD) 104.7 84.4

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

B3LYP/6-31G 86.9 B3LYP/6-311+G** 106.2

M06-2X/6-311+G** SP 90.8 MP2/aptz SP 111.0 MP2/ptz SP 111.2

CCSD(T)/ptz SP 101.3 MLSE(C1)-M06-2X 90.3

paper_G3(MP2,CCSD) 85.3

8

Calculated reaction energetics (kcal/mol) in the triplet electronic state

pathway 3: benzyl alcohol → C6H5CH2O + H　 barrier reaction energy

B3LYP/6-31G 99.8 B3LYP/6-311+G** 128.6

M06-2X/6-311+G** SP 110.8 MP2/aptz SP 117.5

MLSE(C1)-M06-2X 114.0 paper_G3(MP2,CCSD) 114.1 102.9

pathway 4: benzyl alcohol → C6H5CH2 + OH

　 barrier complex reaction energyB3LYP/6-31G 93.8 72.0 75.6

B3LYP/6-311+G** 117.5 98.5 101.1 M06-2X/6-311+G** SP 108.0 85.0 88.5

MP2/aptz SP 132.1 114.1 117.2 MLSE(C1)-M06-2X 104.7 86.9 89.8

paper_G3(MP2,CCSD) 98.6 79.5 81.6

9

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

0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.50 2.75 0.0

50.0

100.0

150.0

200.0

250.0

300.0 1A'2A'1A"2A"

rela

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ener

gy (k

cal/m

ol)

O-H bond distance (Å)

CASSCF/6-31+G**

0.5 1.0 1.5 2.0 2.5 0.0

50.0

100.0

150.0

200.0

250.0 S0-A'T1-A'T2-A'T3-A'T4-A'S1-A'S2-A'T5-A"S3-A"

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol)TD-B3LYP/6-311+G**

10

0.5 1.0 1.5 2.0 2.5 0.0

50.0

100.0

150.0

200.0

S0

T1

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol) B3LYP/6-311+G**

0.5 1.0 1.5 2.0 2.5 0.0

50.0

100.0

150.0

200.0

1A'

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol) CASSCF/6-31+G**

11

0.5 1.0 1.5 2.0 2.5 0.0

50.0

100.0

150.0

200.0

250.0

300.0 S-1A'

S-2A'

T-1A'

T-2A'

S-1A"

S-2A"

T-1A"

T-2A"

O-H bond distance (Å)

CASSCF/6-31+G**

rela

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ener

gy (k

cal/m

ol)

12

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

0.5 1.0 1.5 2.0 2.5 0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0

180.0

200.0 S0T1T2T3T4S1S2

O-H bond distance (Å)

rela

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gy (k

cal/m

ol)

TD-B3LYP/6-311+G**

R=1.621 S TTD-B3LYP 73.4 73.3

B3LYP 73.4 118.0 CASSCF 52.4 99.7

0.5 1.0 1.5 2.0 2.5 0.0

50.0

100.0

150.0

200.0

250.0 1A2A3A4A

O-H bond distance (Å)

CASSCF/6-31+G**

rela

tive

ener

gy (k

cal/m

ol)

unit: kcal/mol

13

0.5 1.0 1.5 2.0 2.5 0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0

180.0

200.0 S0T1

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol) B3LYP/6-311+G**

0.5 1.0 1.5 2.0 2.5 0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0

180.0

200.0 1A

O-H bond distance (Å)

rela

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ener

gy (k

cal/m

ol)

CASSCF/6-31+G**_chk

0.5 1.0 1.5 2.0 2.5 0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0

180.0

200.0 1A

O-H bond distance (Å)

rela

tive

ener

gy (k

cal/m

ol)CASSCF/6-31+G**