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Theoretical studies on the mechanism and kinetic for CH 3 CH 2 O + HO 2 and CH 3 CHOH + HO 2 reactions
Author(s) -
Zhang Tianlei,
Wen Mingjie,
Ju Yan,
Kang Jiaxin,
Wang Rui,
Cao Jia,
Roy Soumendra K.
Publication year - 2019
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3895
Subject(s) - chemistry , reaction rate constant , hydrogen atom abstraction , singlet state , kinetic energy , reaction mechanism , computational chemistry , transition state , elementary reaction , hydrogen , kinetics , excited state , organic chemistry , atomic physics , catalysis , physics , quantum mechanics
The singlet and triplet reaction mechanisms and rate constants for CH 3 CH 2 O + HO 2 and CH 3 CHOH + HO 2 reactions were investigated by employing the high‐level quantum chemical calculations with CBS‐QB3 theoretical method and conventional transition state theory with the Wigner tunneling correction. For CH 3 CH 2 O + HO 2 reaction, four direct hydrogen abstraction processes and five addition‐elimination channels were identified, while two direct hydrogen abstraction routes and nine addition‐elimination channels were found in CH 3 CHOH + HO 2 reaction. The results show that the triplet addition‐elimination channels of CH 3 CH 2 OH + 3 O 2 and CH 3 COOH + H 2 O are, respectively, the most favorable channels for CH 3 CH 2 O + HO 2 and CH 3 CHOH + HO 2 reactions. This is because that they have lower energy barrier and their contribution to the overall rate constants are, respectively, 57% to 86% and 44% to 80%. This work may lead to a better understanding of the mechanism and the kinetic for the singlet and triplet reactions of CH 3 CH 2 O + HO 2 and CH 3 CHOH + HO 2 .