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Theoretical study on the atmospheric reaction of CH 3 SH with O 2
Author(s) -
Bian He,
Xu Bin,
Zhang Honghong,
Wang Qian,
Zhang Huiming,
Zhang Shiguo,
Xia Daohong
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25822
Subject(s) - singlet state , quantum chemical , chemistry , quantum tunnelling , transition state theory , reaction rate constant , computational chemistry , molecule , reaction mechanism , transition state , electron , activation barrier , activation energy , quantum , atomic physics , density functional theory , physics , kinetics , quantum mechanics , excited state , organic chemistry , catalysis
A detailed study on the reaction mechanism of CH 3 SH with O 2 was carried out using quantum chemical methods. Eleven singlet pathways and four triplet pathways were found based on CCSD(T)//M06‐2x calculations. The nature of chemical bonding evolution was also studied using electron localization function and atoms in molecules analysis. Moreover, reaction rate constants were calculated between 200 and 800 K at the level of the transition state theory by Wigner tunneling correction. The results suggest that the main products should be CH 2 SO, H 2 O, CH 3 OH, SO, CH 4 , and SO 2 , respectively, basically coinciding with the experimental results. The corresponding feasible pathways are channels R7, R8, and R9, respectively, with an effective energy barrier of 56.21 kJ/mol. Obviously, given the low energy barrier similar to the main paths mentioned above, the products CH 2 SH and HO 2 should assume a definite proportion in all possible products, although such species were not yet detected in experiment.