Table 1 Comparative analysis of free energy variations pre- and post-reaction and activation free energy values, calculated using B3LYP/6-311++G(d,p) and G4MP2 precision levels
From: A theoretical study on toluene oxidization by OH radical
Reaction | Reaction step | ∆Gʹr (kJ/mol) | ∆Gʹ (kJ/mol) | ∆Gr (kJ/mol) | ∆G (kJ/mol) |
|---|---|---|---|---|---|
Path1 | IS+·OH → IM1 + H2O | − 46.80 | 12.43 | − 64.33 | 28.55 |
IS+·OH → IM2 + H2O | − 45.85 | 13.83 | − 65.96 | 31.15 | |
IS+·OH → IM3 + H2O | − 41.93 | 11.93 | − 64.38 | 29.89 | |
IM1+·OH → FS1 | − 397.08 | – | − 408.85 | – | |
IM2+·OH → FS2 | − 397.32 | – | − 405.70 | – | |
IM3+·OH → FS3 | − 401.28 | – | − 406.93 | – | |
Path2 | IS+·OH → IM4 | − 40.51 | 7.96 | − 63.82 | 16.92 |
IS+·OH → IM5 | − 46.43 | 0.93 | − 60.74 | 14.37 | |
IS+·OH → IM6 | − 39.29 | 4.39 | − 56.39 | 17.63 | |
IS+·OH → IM7 | − 44.27 | 0.17 | − 58.95 | 13.77 | |
IM4 → FS4 | 192.82 | 222.41 | 216.64 | 246.52 | |
IM5 → FS5.1 | 216.75 | 223.61 | 215.58 | 227.53 | |
IM5 → FS5.2 | 187.32 | 199.05 | 232.04 | 242.19 | |
IM6 → FS6.1 | 205.76 | 216.80 | 226.10 | 240.04 | |
IM6 → FS6.2 | 204.33 | 214.67 | 222.79 | 236.53 | |
IM7 → FS7 | 211.42 | 218.55 | 227.04 | 239.30 | |
Path3-1 | IS+·OH → IM8 + H2O | − 139.78 | 9.07 | − 150.46 | 5.18 |
IM8+·OH → IM9 | − 268.74 | – | − 295.31 | – | |
IM9+·OH → IM10.1 + H2O | − 174.50 | 8.92 | − 167.12 | 16.55 | |
IM9+·OH → IM10.2 + H2O | − 85.73 | 9.27 | − 102.18 | 28.12 | |
IM10.1+·OH → IM11.1 | − 279.88 | – | − 306.41 | – | |
IM10.2+·OH → IM11.2 | − 101.44 | – | − 117.95 | – | |
IM11.1 → IM12 + H2O | − 49.50 | 152.32 | − 43.18 | 161.15 | |
IM11.2 → IM12 + H2O | − 310.29 | 186.06 | − 315.06 | 189.43 | |
IM12+·OH → IM13 + H2O | − 107.12 | – | − 126.61 | – | |
IM13+·OH → FS8 | − 390.01 | – | − 395.59 | – | |
Path3-2 | FS8+·OH → IM14 | − 27.50 | 10.29 | − 43.83 | 34.85 |
FS8+·OH → IM15 | − 63.42 | 8.01 | − 61.08 | 27.16 | |
FS8+·OH → IM16 | − 37.44 | 11.17 | − 47.41 | 30.53 | |
FS8+·OH → IM17 | − 49.67 | 10.02 | − 56.46 | 29.93 | |
IM14 → FS9 | 202.35 | 205.10 | 222.53 | 233.54 | |
IM15 → FS10.1 | 200.70 | 206.34 | 231.83 | 255.92 | |
IM15 → FS10.2 | 247.03 | 244.02 | 250.94 | 234.63 | |
IM16 → FS11.1 | 210.28 | 228.05 | 237.66 | 247.57 | |
IM16 → FS11.2 | 196.15 | 216.29 | 213.82 | 240.08 | |
IM17 → FS12 | 208.44 | 212.50 | 231.14 | 241.39 |