Supporting information
-for-
Computational Study on the Mechanism and Kinetics for the Reaction between HCHO and HO2
Rui Wang a, Yili Li a, Fukai Fenga, Kai Zhang a, Roy Soumendra Kumara
Ting Donga , Zhiyin Wanga, Qiong Xua, Tianlei Zhanga,[(], Zhuqing Wang b *
a School of Chemical & Environment Science, Shaanxi University of Technology, Hanzhong, Shaanxi 723001, China
b Analytical and Testing Center, Sichuan University of Science & Engineering, Sichuan, China 643000, China
Table S1 The value of S2> after spin annihilation and T1 diagnostic values for all the species involved in the HCHO + HO2 reaction
CH2O / 0.0001 / HO2 / 0.7500 / TS1 / 0.7502 / TS1a / 0.7501
CH3O / 0.7502 / O2 / 2.000 / TS2 / 0.7503 / TS2a / 0.7506
CH2OH / 0.7500 / IM3 / 0.7502 / TS3 / 0.7506 / IMF3 / 0.7509
TS3a / 0.7504 / IMF3a / 0.7502 / HCO / 0.7503 / H2O2 / 0.0000
IM4 / 0.7500 / TS4 / 0.7503 / HCOH / 0.0000 / HO2 / 0.7502
TS5 / 0.7502 / H2 / 0.0000 / IM6 / 0.7500 / TS6 / 0.7502
HCOO / 0.7500 / H2O / 0.0000 / IM7 / 0.7500 / TS7 / 0.7500
CH3 / 0.7500 / O3 / 0.0000 / IM8 / 0.7500 / TS8a / 0.7500
IMF8a / 0.7500 / IM8b / 0.7500 / TS8b / 0.7500 / HOCH2OO / 0.7500
Table S2 Rate constants (cm3×molecule-1×s-1) for direct hydrogen abstraction channels of CH3O + HO2, CH2OH + O2, HOC + H2O2 and HCOH + HO2 formations in the HCHO + HO2 reaction
275 / 1.64E-39 / 3.50E-39 / 1.96E-37 / 1.44E-37 / 5.91E-22 / 1.01E-21 / 5.13E-66
300 / 1.76E-37 / 5.62E-35 / 1.95E-35 / 1.46E-35 / 1.82E-21 / 3.03E-21 / 8.49E-62
325 / 9.37E-36 / 3.94E-34 / 9.74E-34 / 7.44E-34 / 5.41E-21 / 8.73E-21 / 3.35E-58
333 / 2.96E-35 / 2.39E-33 / 3.02E-33 / 2.32E-33 / 7.57E-21 / 1.21E-20 / 3.68E-57
400 / 7.69E-32 / 1.27E-32 / 6.94E-30 / 5.53E-30 / 9.70E-20 / 1.43E-19 / 4.93E-50
500 / 2.14E-28 / 6.03E-32 / 1.72E-26 / 1.42E-26 / 1.87E-18 / 2.50E-18 / 7.18E-43
600 / 4.65E-26 / 2.57E-31 / 3.48E-24 / 2.96E-24 / 1.69E-17 / 2.13E-17 / 4.85E-38
625 / 1.39E-25 / 1.00E-30 / 3.16E-23 / 2.13E-23 / 2.89E-17 / 3.13E-17 / 4.55E-37
650 / 3.81E-25 / 3.58E-30 / 5.46E-23 / 3.76E-23 / 5.19E-17 / 5.53E-17 / 3.62E-36
675 / 9.76E-25 / 1.18E-29 / 9.38E-23 / 8.16E-23 / 7.29E-17 / 8.13E-17 / 2.48E-35
700 / 2.35E-24 / 7.47E-28 / 1.67E-22 / 1.45E-22 / 9.22E-17 / 9.52E-17 / 1.49E-34
725 / 5.34E-24 / 2.12E-26 / 3.67E-22 / 3.37E-22 / 9.45E-17 / 9.93E-17 / 7.92E-34
750 / 1.15E-23 / 3.36E-25 / 5.27E-22 / 5.17E-22 / 1.13E-16 / 1.16E-16 / 3.79E-33
775 / 2.38E-21 / 7.26E-25 / 1.47E-21 / 1.27E-21 / 2.13E-16 / 2.36E-16 / 1.64E-32
800 / 4.71E-20 / 9.47E-25 / 3.24E-21 / 2.84E-21 / 3.65E-16 / 4.24E-16 / 6.53E-32
900 / 5.09E-19 / 2.48E-23 / 3.40E-20 / 3.01E-20 / 1.12E-15 / 1.27E-15 / 7.81E-30
1000 / 3.55E-18 / 6.02E-23 / 2.31E-19 / 2.07E-19 / 2.89E-15 / 3.21E-15 / 3.74E-28
1100 / 1.80E-17 / 1.38E-22 / 1.15E-18 / 1.03E-18 / 6.49E-15 / 7.09E-15 / 9.16E-27
1200 / 1.45E-16 / 2.98E-22 / 4.46E-18 / 4.04E-18 / 1.31E-14 / 1.41E-14 / 1.35E-25
1250 / 2.85E-16 / 6.15E-22 / 8.46E-18 / 8.11E-18 / 1.51E-14 / 1.81E-14 / 4.47E-25
1300 / 4.85E-16 / 1.21E-21 / 1.44E-17 / 1.73E-20 / 2.31E-14 / 3.41E-14 / 1.36E-24
1350 / 1.36E-15 / 2.30E-21 / 2.54E-17 / 2.36E-17 / 3.81E-14 / 4.13E-14 / 3.80E-24
1400 / 3.66E-15 / 4.21E-21 / 4.14E-17 / 3.66E-17 / 4.21E-14 / 5.41E-14 / 9.95E-24
1450 / 7.86E-15 / 7.46E-21 / 7.12E-17 / 6.94E-17 / 5.71E-14 / 6.31E-14 / 2.45E-23
1500 / 1.36E-14 / 1.28E-20 / 9.85E-17 / 9.04E-17 / 6.95E-14 / 7.27E-14 / 5.70E-23
1550 / 1.79E-14 / 2.38E-20 / 1.12E-16 / 1.11E-16 / 8.15E-14 / 9.12E-14 / 1.26E-22
1600 / 3.65E-14 / 4.71E-20 / 2.20E-16 / 2.02E-16 / 1.02E-13 / 1.13E-13 / 2.66E-22
1650 / 4.13E-14 / 5.09E-19 / 3.20E-16 / 3.12E-16 / 1.13E-13 / 1.23E-13 / 5.40E-22
1700 / 5.56E-14 / 3.55E-18 / 4.52E-16 / 4.52E-16 / 1.39E-13 / 1.53E-13 / 1.05E-21
1750 / 6.46E-14 / 1.80E-17 / 6.52E-16 / 6.32E-16 / 2.09E-13 / 2.31E-13 / 1.98E-21
1800 / 7.42E-14 / 3.45E-17 / 8.62E-16 / 8.02E-16 / 2.38E-13 / 2.44E-13 / 3.61E-21
kTS1 and kTS1a is the rate constant for the process of HO2 + HCHO → TS1 → CH3O + HO2 and HO2 + HCHO → TS1a →CH3O + HO2, respectively; kTS2 and kTS2a is the rate constant for the process of HO2 + HCHO → TS2 →CH2OH + O2 and HO2 + HCHO → TS2a →CH2OH + O2, respectively; kTS3 and kTS3a is the rate constant for the process of HO2 + HCHO → TS3 →HOC + H2O2 and HO2 + HCHO → TS3a →HOC + H2O2, respectively; kR4 is the rate constant for the process of HO2 + HCHO → TS4 → HCOH + HO2.
Table S3 Rate constants (cm3×molecule-1×s-1) for indirect hydrogen abstraction channels and addition processes of O2 + H2 + HCO, HOOC + H2O, CH3 + O3 and HOCH2OO formations in the HCHO + HO2 reaction
T/K / kR5 / kR6 / kR7 / kTS8 / kTS8a / kTS8b275 / 7.93E-56 / 3.38E-121 / 1.90E-89 / 8.93E-59 / 5.12E-14 / 1.81E-96
300 / 3.02E-52 / 1.44E-112 / 2.84E-83 / 2.67E-55 / 5.89E-14 / 1.10E-89
325 / 3.29E-49 / 3.79E-105 / 4.82E-78 / 2.73E-52 / 6.34E-14 / 6.06E-84
333 / 2.48E-48 / 5.38E-103 / 1.56E-76 / 2.05E-51 / 6.48E-14 / 2.75E-82
400 / 2.48E-42 / 2.98E-88 / 2.95E-66 / 2.21E-45 / 1.31E-13 / 5.19E-71
500 / 2.63E-36 / 1.82E-73 / 5.29E-56 / 2.77E-39 / 1.51E-13 / 8.88E-60
600 / 3.10E-32 / 1.55E-63 / 3.95E-49 / 3.67E-35 / 2.31E-13 / 2.91E-52
625 / 4.60E-31 / 1.53E-61 / 6.95E-46 / 2.49E-34 / 3.81E-13 / 9.34E-51
650 / 7.43E-31 / 1.07E-59 / 3.43E-45 / 1.47E-33 / 4.21E-13 / 2.31E-49
675 / 6.10E-30 / 5.48E-58 / 2.15E-44 / 7.60E-33 / 5.71E-13 / 4.50E-48
700 / 2.74E-29 / 2.13E-56 / 3.44E-44 / 3.52E-32 / 6.95E-13 / 7.14E-47
725 / 3.45E-28 / 6.47E-55 / 5.16E-42 / 1.47E-31 / 8.15E-13 / 9.37E-46
750 / 5.62E-28 / 1.57E-53 / 7.24E-41 / 5.63E-31 / 1.02E-12 / 1.04E-44
775 / 2.12E-27 / 3.13E-52 / 9.84E-42 / 1.98E-30 / 1.13E-12 / 9.90E-44
800 / 4.76E-27 / 5.17E-51 / 1.84E-40 / 6.45E-30 / 1.39E-12 / 8.21E-43
900 / 2.76E-25 / 8.44E-47 / 1.53E-37 / 3.90E-28 / 2.09E-12 / 1.23E-39
1000 / 7.41E-24 / 2.07E-43 / 3.44E-35 / 1.08E-26 / 2.38E-12 / 4.37E-37
1100 / 1.13E-22 / 1.27E-40 / 2.97E-33 / 1.68E-25 / 3.36E-12 / 5.49E-35
1200 / 1.57E-21 / 2.75E-38 / 1.85E-31 / 1.70E-24 / 4.63E-12 / 3.15E-33
1250 / 4.12E-21 / 2.96E-37 / 5.25E-31 / 4.76E-24 / 4.92E-11 / 1.88E-32
1300 / 7.95E-21 / 2.67E-36 / 3.45E-30 / 1.24E-23 / 6.57E-11 / 9.85E-32
1350 / 3.44E-20 / 2.06E-35 / 8.04E-30 / 3.00E-23 / 7.58E-11 / 4.58E-31
1400 / 4.66E-20 / 1.37E-34 / 4.75E-29 / 6.89E-23 / 9.41E-11 / 1.92E-30
1450 / 8.35E-20 / 8.10E-34 / 7.24E-29 / 1.50E-22 / 1.29E-10 / 7.29E-30
1500 / 1.45E-19 / 4.26E-33 / 1.85E-28 / 3.10E-22 / 3.42E-10 / 2.54E-29
1550 / 4.93E-19 / 2.02E-32 / 5.24E-28 / 6.15E-22 / 6.98E-10 / 8.22E-29
1600 / 5.47E-19 / 8.72E-32 / 4.45E-27 / 1.17E-21 / 8.59E-10 / 2.47E-28
1650 / 7.17E-19 / 3.46E-31 / 8.33E-27 / 2.16E-21 / 9.98E-10 / 6.99E-28
1700 / 2.31E-18 / 1.27E-30 / 6.45E-26 / 3.85E-21 / 1.03E-09 / 1.86E-27
1750 / 5.14E-18 / 4.33E-30 / 2.83E-26 / 6.65E-21 / 2.45E-09 / 4.70E-27
1800 / 6.60E-18 / 1.39E-29 / 1.52E-25 / 1.12E-20 / 4.94E-09 / 1.13E-26
kR5 is the rate constant for the process of HO2 + HCHO → TS5 → O2 + H2 + HCO; kR6 is the rate constant for the process of HO2 + HCHO → TS6 → HOOC + H2O; kR7 is the rate constant for the process of HO2 + HCHO → TS7 → CH3 + O3; kTS8, kTS8a and kTS8b is the rate constant for the process of HO2 + HCHO → TS8 →HOCH2OO, HO2 + HCHO → IM8a → TS8a →IMF8a→ HOCH2OO and HO2 + HCHO → TS8b → HOCH2OO respectively.
Table S4 Rate constants (cm3×molecule-1×s-1) for channels of CH3O + HO2 (kR1), CH2OH + O2 (kR2), HOC + H2O2 (kR3), HCOH + HO2 (kR4), O2 + H2 + HCO (kR5), HOOC + H2O (kR6), CH3 + O3 (kR7), and HOCH2OO (kR8) formations in the HCHO + HO2 reaction within the temperature of 275-1800 K along with the available experimental values
275 / 5.13E-39 / 3.39E-37 / 1.60E-21 / 5.14E-66 / 7.93E-56 / 3.38E-121 / 1.90E-89 / 5.12E-14(9.41E-14)
300 / 5.64E-35 / 3.41E-35 / 4.85E-21 / 8.50E-62 / 3.02E-52 / 1.44E-112 / 2.84E-83 / 5.89E-14(7.79E-14)
325 / 4.03E-34 / 1.72E-33 / 1.41E-20 / 3.35E-58 / 3.29E-49 / 3.79E-105 / 4.82E-78 / 6.34E-14(6.64E-14)
333 / 2.42E-33 / 5.33E-33 / 1.97E-20 / 3.68E-57 / 2.48E-48 / 5.38E-103 / 1.56E-76 / 6.48E-14(6.34E-14)
400 / 8.96E-32 / 1.25E-29 / 2.40E-19 / 4.93E-50 / 2.48E-42 / 2.98E-88 / 2.95E-66 / 1.31E-13
500 / 2.14E-28 / 3.14E-26 / 4.37E-18 / 7.18E-43 / 2.63E-36 / 1.82E-73 / 5.29E-56 / 1.51E-13
600 / 4.65E-26 / 6.44E-24 / 3.82E-17(8.63E-17) / 4.85E-38 / 3.10E-32 / 1.55E-63 / 3.95E-49 / 2.31E-13
625 / 1.39E-25 / 5.29E-23 / 6.02E-17(1.34E-16) / 4.55E-37 / 4.60E-31 / 1.53E-61 / 6.95E-46 / 3.81E-13
650 / 3.81E-25 / 9.22E-23 / 1.07E-16(2.01E-16) / 3.62E-36 / 7.43E-31 / 1.07E-59 / 3.43E-45 / 4.21E-13
675 / 9.76E-25 / 1.75E-22 / 1.54E-16(2.92E-16) / 2.48E-35 / 6.10E-30 / 5.48E-58 / 2.15E-44 / 5.71E-13
700 / 2.35E-24 / 3.12E-22 / 1.87E-16(4.13E-16) / 1.49E-34 / 2.74E-29 / 2.13E-56 / 3.44E-44 / 6.95E-13
725 / 5.36E-24 / 7.05E-22 / 1.94E-16(5.72E-16) / 7.91E-34 / 3.45E-28 / 6.47E-55 / 5.16E-42 / 8.15E-13
750 / 1.19E-23 / 1.04E-21 / 2.29E-16(7.74E-16) / 3.79E-33 / 5.62E-28 / 1.57E-53 / 7.24E-41 / 1.02E-12
775 / 2.38E-21 / 2.75E-21 / 4.49E-16(1.03E-15) / 1.64E-32 / 2.12E-27 / 3.13E-52 / 9.84E-42 / 1.13E-12
800 / 4.71E-20 / 6.08E-21 / 7.89E-16(1.34E-15) / 6.53E-32 / 4.76E-27 / 5.17E-51 / 1.84E-40 / 1.39E-12
900 / 5.09E-19 / 6.41E-20 / 2.39E-15(3.34E-15) / 7.81E-30 / 2.76E-25 / 8.44E-47 / 1.53E-37 / 2.09E-12
1000 / 3.55E-18 / 4.38E-19 / 6.09E-15(6.94E-15) / 3.74E-28 / 7.41E-24 / 2.07E-43 / 3.44E-35 / 2.38E-12
1100 / 1.80E-17 / 2.18E-18 / 1.36E-14 / 9.16E-27 / 1.13E-22 / 1.27E-40 / 2.97E-33 / 3.36E-12
1200 / 1.45E-16(1.86E-15) / 8.50E-18 / 2.73E-14 / 1.36E-25 / 1.57E-21 / 2.75E-38 / 1.85E-31 / 4.63E-12
1250 / 2.85E-16(2.56E-15) / 1.66E-17 / 3.33E-14 / 4.47E-25 / 4.12E-21 / 2.96E-37 / 5.25E-31 / 4.92E-11
1300 / 4.85E-16 / 1.44E-17 / 5.73E-14 / 1.36E-24 / 7.95E-21 / 2.67E-36 / 3.45E-30 / 6.57E-11
1350 / 1.36E-15(4.53E-15) / 4.90E-17 / 7.94E-14 / 3.80E-24 / 3.44E-20 / 2.06E-35 / 8.04E-30 / 7.58E-11
1400 / 3.66E-15(4.53E-15) / 7.80E-17 / 9.63E-14 / 9.95E-24 / 4.66E-20 / 1.37E-34 / 4.75E-29 / 9.41E-11
1450 / 7.86E-15(7.40E-15) / 1.41E-16 / 1.20E-13 / 2.45E-23 / 8.35E-20 / 8.10E-34 / 7.24E-29 / 1.29E-10
1500 / 1.36E-14(9.23E-15) / 1.89E-16 / 1.42E-13 / 5.70E-23 / 1.45E-19 / 4.26E-33 / 1.85E-28 / 3.42E-10
1550 / 1.79E-14(1.14E-14) / 2.23E-16 / 1.73E-13 / 1.26E-22 / 4.93E-19 / 2.02E-32 / 5.24E-28 / 6.98E-10
1600 / 3.65E-14(1.14E-14) / 4.22E-16 / 2.15E-13 / 2.66E-22 / 5.47E-19 / 8.72E-32 / 4.45E-27 / 8.59E-10
1650 / 4.13E-14(1.65E-14) / 6.32E-16 / 2.36E-13 / 5.40E-22 / 7.17E-19 / 3.46E-31 / 8.33E-27 / 9.98E-10
1700 / 5.56E-14(1.65E-14) / 9.03E-16 / 2.92E-13 / 1.05E-21 / 2.31E-18 / 1.27E-30 / 6.45E-26 / 1.03E-09
1750 / 6.46E-14(2.31E-14) / 1.28E-15 / 4.40E-13 / 1.98E-21 / 5.14E-18 / 4.33E-30 / 2.83E-26 / 2.45E-09
1800 / 7.42E-14(2.69E-14) / 1.66E-15 / 4.83E-13 / 3.61E-21 / 6.60E-18 / 1.39E-29 / 1.52E-25 / 4.94E-09
Table S5 The branching ratios of channel R3 and R8 in the HCHO and HO2 reaction
275 / 1.60E-21 / 5.12E-14 / 5.12E-14 / 0.000 / 1.000
300 / 4.85E-21 / 5.89E-14 / 5.89E-14 / 0.000 / 1.000
325 / 1.41E-20 / 6.34E-14 / 6.34E-14 / 0.000 / 1.000
333 / 1.97E-20 / 6.48E-14 / 6.48E-14 / 0.000 / 1.000
400 / 2.40E-19 / 1.31E-13 / 1.31E-13 / 0.000 / 1.000
500 / 4.37E-18 / 1.51E-13 / 1.51E-13 / 0.000 / 1.000
600 / 3.82E-17 / 2.31E-13 / 2.31E-13 / 0.000 / 1.000
625 / 6.02E-17 / 3.81E-13 / 3.81E-13 / 0.000 / 1.000
650 / 1.07E-16 / 4.21E-13 / 4.21E-13 / 0.000 / 1.000
675 / 1.54E-16 / 5.71E-13 / 5.71E-13 / 0.000 / 1.000
700 / 1.87E-16 / 6.95E-13 / 6.95E-13 / 0.000 / 1.000
725 / 1.94E-16 / 8.15E-13 / 8.15E-13 / 0.000 / 1.000
750 / 2.29E-16 / 1.02E-12 / 1.02E-12 / 0.000 / 1.000
775 / 4.49E-16 / 1.13E-12 / 1.13E-12 / 0.000 / 1.000
800 / 7.89E-16 / 1.39E-12 / 1.39E-12 / 0.001 / 0.999
900 / 2.39E-15 / 2.09E-12 / 2.09E-12 / 0.001 / 0.999
1000 / 6.09E-15 / 2.38E-12 / 2.39E-12 / 0.003 / 0.997
1100 / 1.36E-14 / 3.36E-12 / 3.37E-12 / 0.004 / 0.996
1200 / 2.73E-14 / 4.63E-12 / 4.66E-12 / 0.006 / 0.994
1250 / 3.33E-14 / 4.92E-11 / 4.92E-11 / 0.001 / 0.999
1300 / 5.73E-14 / 6.57E-11 / 6.58E-11 / 0.001 / 0.999
1350 / 7.94E-14 / 7.58E-11 / 7.59E-11 / 0.001 / 0.999
1400 / 9.63E-14 / 9.41E-11 / 9.42E-11 / 0.001 / 0.999
1450 / 1.20E-13 / 1.29E-10 / 1.29E-10 / 0.001 / 0.999
1500 / 1.42E-13 / 3.42E-10 / 3.42E-10 / 0.000 / 1.000
1550 / 1.73E-13 / 6.98E-10 / 6.98E-10 / 0.000 / 1.000
1600 / 2.15E-13 / 8.59E-10 / 8.59E-10 / 0.000 / 1.000
1650 / 2.36E-13 / 9.98E-10 / 9.98E-10 / 0.000 / 1.000
1700 / 2.92E-13 / 1.03E-09 / 1.03E-09 / 0.000 / 1.000
1750 / 4.40E-13 / 2.45E-09 / 2.45E-09 / 0.000 / 1.000
1800 / 4.83E-13 / 4.94E-09 / 4.94E-09 / 0.000 / 1.000
[(]* Corresponding authors. Tel: +86-0916-2641083, Fax: +86-0916-2641083.
e-mail: (T. L Zhang).