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Mechanism and Kinetics for the Reaction of NCS and OH Radicals
Author(s) -
Liu PengJu,
Zhao Min,
Chang MngFei,
Zhao YanLing,
Su ZhongMin,
Wang RongShun
Publication year - 2004
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20040220619
Subject(s) - chemistry , reaction rate constant , radical , kinetics , transition state theory , activation energy , atmospheric temperature range , thermodynamics , path (computing) , reaction mechanism , range (aeronautics) , density functional theory , chemical kinetics , computational chemistry , catalysis , quantum mechanics , organic chemistry , physics , materials science , computer science , composite material , programming language
The mechanism and dynamical properties for the reaction of NCS and OH radicals have been investigated theoretically. The minimum energy paths (MEP) of the reaction were calculated using the density functional theory (DFT) at the B3LYP/6‐3 11 +G**level, and the energies along the MEP were further refined at the QCISD(T)/6‐311 +G** level. As a result, the reaction mechanism of the title reaction involves three channels, producing HCS+NO and HNC+SO products, respectively. Path I and path LI are competitive, with some advantages for path I in kinetics.As for path 111. it looks difficult to react for its high energy barrier. Moreover, the rate constant have been calculated over the temperature range of 800‐2500 K using canonical variational transition‐state theory (CVT). It was found that the rate constants for both path I and path II are negatively dependent on temperature, which is similar with the experimental results for reactions of NCS with NO and NO*, and the variational effect for the rate constant calculation plays an important role in whole temperature range.