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Computational Study on the Mechanisms and Pathways of the Atmospheric NH 2 + BrO Reaction
Author(s) -
Zhang Yunju,
He Bing,
Sun Yuxi
Publication year - 2019
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201902866
Subject(s) - chemistry , reaction rate constant , hydrogen atom abstraction , perturbation theory (quantum mechanics) , transition state theory , atmospheric pressure , basis set , computational chemistry , kinetic energy , product distribution , thermodynamics , radical , analytical chemistry (journal) , kinetics , density functional theory , organic chemistry , physics , meteorology , quantum mechanics , catalysis
The NH 2 radical reaction with BrO was characterized by combining the second‐order Møller–Plesset perturbation theory (MP2) with a 6–311++G(d,p) basis set, followed by kinetic analyses using the Rice–Ramsperger–Kassel–Marcus (RRKM) theory and transition‐state (TST) theory to forecast the product distribution and thermal rate coefficients. Addition/elimination and H‐abstraction mechanisms are observed, and three products are identified: P1 (HBr + HNO), P2 (NBr + H 2 O) and P3 ( 3 NH + HOBr). At atmospheric pressure, P1 (HBr + HNO), generated by the association/elimination channel, represents the primary products between 200–500 K; the direct H‐abstraction leading to P3 ( 3 NH + HOBr) plays a significant role above 500 K. However, at the high‐pressure limit, IM1 [BrONH 2 ] generated by collisional stabilization is dominant between 200–500 K; the direct H‐abstraction leading to P3 ( 3 NH + HOBr) was the major channel at high‐temperature. Moreover, the total rate constants are pressure independent; however the individual rate constants are sensitive to pressure.