1. Benzyl Alcohol 2012/07/17

2. Geometries at the B3LYP/aug-cc-pVTZ level dHOCCdOCC5CrOH relative energy (kcal/mol) including ZPE 1gauche cis54.855.40.9630.0 2173.9  18.8 0.9611.00.8 3  176.5 10.70.9601.00.8 4planar180.00.00.9601.00.8 1 (gauche cis) 2 3 4 (planar) (Cs symmetry) 1

3. Dissociation pathways in the ground state at the G3(MP2, CCSD) and CCSD(T)/ptz (including B3LYP/aptz ZPE) in the parentheses 2 C 6 H 5 CH (triplet state is 3.2 kcal/mol lower than singlet state at CCSD(T)/ptz level)

4. Calculated reaction energetics (kcal/mol, including ZPE) in the ground electronic state 3 pathway 1: benzyl alcohol → C 6 H 5 CH 2 O + H reaction energy B3LYP/6-31G90.2 B3LYP/6-311+G**119.0 B3LYP/aug-cc-pVTZ97.8 M06-2X/6-311+G** SP101.2 MP2/aptz SP108.0 CCSD(T)/ptz SP101.4 MLSE(C1)-M06-2X104.4 paper_G3(MP2,CCSD)102.9 pathway 2: benzyl alcohol → C 6 H 5 CHOH + H reaction energy B3LYP/6-31G79.3 B3LYP/6-311+G**100.3 B3LYP/aug-cc-pVTZ77.9 M06-2X/6-311+G** SP82.1 MP2/aptz SP106.0 CCSD(T)/ptz SP83.6 MLSE(C1)-M06-2X84.8 paper_G3(MP2,CCSD)84.4 pathway 3: benzyl alcohol → C 6 H 5 CH 2 + OH reaction energy B3LYP/6-31G69.2 B3LYP/6-311+G**94.7 B3LYP/aug-cc-pVTZ73.0 M06-2X/6-311+G** SP82.1 MP2/aptz SP110.8 CCSD(T)/ptz SP80.6 MLSE(C1)-M06-2X83.4 paper_G3(MP2,CCSD)81.6 pathway 4: benzyl alcohol → C 6 H 5 + CH 2 OH reaction energy B3LYP/6-31G93.7 B3LYP/6-311+G**111.1 B3LYP/aug-cc-pVTZ88.7 M06-2X/6-311+G** SP97.4 MP2/aptz SP128.1 CCSD(T)/ptz SP99.3 MLSE(C1)-M06-2X101.1 paper_G3(MP2,CCSD)98.4

5. Calculated reaction energetics (kcal/mol, including ZPE) in the ground electronic state 4 pathway 5: benzyl alcohol → C 6 H 6 + CH 2 O barrierreaction energy B3LYP/6-31G83.212.0 B3LYP/6-311+G**103.532.3 B3LYP/aug-cc-pVTZ81.110.5 M06-2X/6-311+G** SP85.517.6 MP2/aptz SP83.218.2 CCSD(T)/ptz SP85.814.7 MLSE(C1)-M06-2X83.716.8 paper_G3(MP2,CCSD)88.815.2 pathway 6: benzyl alcohol → C 6 H 5 CH(singlet, triplet) + H 2 O barriercomplexreaction energy C 6 H 5 CH(S) + H 2 OC 6 H 5 CH(T) + H 2 O B3LYP/6-31G71.870.885.674.5 B3LYP/6-311+G**92.186.294.488.9 B3LYP/aug-cc-pVTZ70.565.272.566.8 M06-2X/6-311+G** SP80.771.280.172.6 MP2/aptz SP79.173.081.499.1 CCSD(T)/ptz SP76.770.077.574.3 MLSE(C1)-M06-2X75.369.076.774.7 paper_G3(MP2,CCSD)75.271.476.5 C 6 H 5 CH (triplet state is 3.2 kcal/mol lower than singlet state at CCSD(T)/ptz level)

6. Possible excited states of dissociation products photo energy: 147.8 kcal/mol 5 pathway 1: benzyl alcohol → C 6 H 5 CH 2 O + H reaction energy: 101.4 kcal/mol 以 doublet state C 6 H 5 CH 2 O 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH 2 O ground state A" Excited state 1 A" Excited state 2 A' Excited state 3 A' eV 0.472.052.28 kcal/mol0.0010.7647.2652.49 pathway 2: benzyl alcohol → C 6 H 5 CHOH + H reaction energy: 83.6 kcal/mol 以 doublet state C 6 H 5 CHOH 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CHOH ground state A" Excited state 1 A' Excited state 2 A' Excited state 3 A" eV 2.843.353.40 kcal/mol0.0065.5977.2378.34 pathway 3: benzyl alcohol → C 6 H 5 CH 2 + OH reaction energy: 80.6 kcal/mol 以 doublet state C 6 H 5 CH 2 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH 2 ground state B1 Excited state 1 B2 Excited state 2 A1 eV 3.173.39 kcal/mol0.0073.0878.23

7. 6 Possible excited states of dissociation products photo energy: 147.8 kcal/mol pathway 6: benzyl alcohol → C 6 H 5 CH + H 2 O reaction energy: 77.5(S), 74.3(T) kcal/mol 以 triplet state C 6 H 5 CH 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH Triplet ground state-A" Excited state 1 A' Excited state 2 A' eV 3.283.53 kcal/mol0.0075.7081.48 以 singlet state C 6 H 5 CH 結構計算 TD-B3LYP/6-311+G** C 6 H 5 CH 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 1.162.973.093.68 kcal/mol  16.49 0.0026.6768.3771.2784.89

8. Dissociation pathways in the triplet state at the G3(MP2, CCSD) and CCSD(T)/ptz (including B3LYP/aptz ZPE) in the parentheses 7

9. Calculated reaction energetics (kcal/mol, relative to the singlet ground state) in the triplet electronic state 8 benzyl alcohol(singlet) → benzyl alcohol(triplet) S-T gap B3LYP/6-31G82.5 B3LYP/6-311+G**101.7 B3LYP/aug-cc-pVTZ80.4 M06-2X/6-311+G** SP86.3 MP2/aptz SP106.5 MP2/ptz SP106.8 CCSD(T)/ptz SP96.9 MLSE(C1)-M06-2X85.9 paper_G3(MP2,CCSD)85.3 pathway 1: benzyl alcohol → C 6 H 5 + CH 2 OH barrierreaction energy B3LYP/6-31G107.793.7 B3LYP/6-311+G**125.8111.1 B3LYP/aug-cc-pVTZ104.188.7 M06-2X/6-311+G** SP110.597.4 MP2/aptz SP139.6128.1 CCSD(T)/ptz SP112.299.3 MLSE(C1)-M06-2X113.1101.1 paper_G3(MP2,CCSD)118.398.4 pathway 2: benzyl alcohol → C 6 H 5 CHOH + H barrierreaction energy B3LYP/6-31G79.3 B3LYP/6-311+G**100.3 B3LYP/aug-cc-pVTZ77.9 M06-2X/6-311+G** SP82.1 MP2/aptz SP106.0 CCSD(T)/ptz SP83.6 MLSE(C1)-M06-2X84.8 paper_G3(MP2,CCSD)104.784.4

10. Calculated reaction energetics (kcal/mol, relative to the singlet ground state) in the triplet electronic state 9 pathway 3: benzyl alcohol → C 6 H 5 CH 2 O + H barrierreaction energy B3LYP/6-31G90.2 B3LYP/6-311+G**119.0 B3LYP/aug-cc-pVTZ97.8 M06-2X/6-311+G** SP101.2 MP2/aptz SP108.0 CCSD(T)/ptz SP101.4 MLSE(C1)-M06-2X104.4 paper_G3(MP2,CCSD)114.1102.9 pathway 4: benzyl alcohol → C 6 H 5 CH 2 + OH barriercomplexreaction energy B3LYP/6-31G89.066.769.2 B3LYP/6-311+G**112.693.294.7 B3LYP/aug-cc-pVTZ91.271.973.0 M06-2X/6-311+G** SP103.179.782.1 MP2/aptz SP127.3108.8110.8 CCSD(T)/ptz SP100.278.780.6 MLSE(C1)-M06-2X99.981.683.4 paper_G3(MP2,CCSD)98.679.581.6

11. The energies (kcal/mol) along the O-H bond distance in hydroxyl group of the planar conformation 10

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