benzyl alcohol
DESCRIPTION
Benzyl Alcohol. 2012/07/11. Geometries at the B3LYP/ aug -cc- pVTZ level. 2. 1 ( gauche cis ). 4 ( plana r) (Cs symmetry). 3. Dissociation pathways in the ground electronic state at the MLSE(C1)-M06-2X. Calculated reaction energetics (kcal/ mol ) in the ground electronic state. - PowerPoint PPT PresentationTRANSCRIPT
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
tive
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
tive
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
tive
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
tive
ener
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
tive
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**