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Mechanism and rate constants of the CH 2 + CH 2 CO reactions in triplet and singlet states: A theoretical study
Author(s) -
Savchenkova Anna S.,
Semenikhin Alexander S.,
Chechet Ivan V.,
Matveev Sergey G.,
Konnov Alexander A.,
Mebel Alexander M.
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25613
Subject(s) - ketene , chemistry , intersystem crossing , singlet state , reaction rate constant , methylene , triplet state , singlet fission , photochemistry , isomerization , ab initio , computational chemistry , transition state , arrhenius equation , density functional theory , molecule , activation energy , atomic physics , excited state , physics , organic chemistry , kinetics , catalysis , quantum mechanics
Ab initio and density functional CCSD(T)‐F12/cc‐pVQZ‐f12//B2PLYPD3/6‐311G** calculations have been performed to unravel the reaction mechanism of triplet and singlet methylene CH 2 with ketene CH 2 CO. The computed potential energy diagrams and molecular properties have been then utilized in Rice–Ramsperger–Kassel–Marcus‐Master Equation (RRKM‐ME) calculations of the reaction rate constants and product branching ratios combined with the use of nonadiabatic transition state theory for spin‐forbidden triplet‐singlet isomerization. The results indicate that the most important channels of the reaction of ketene with triplet methylene lead to the formation of the HCCO + CH 3 and C 2 H 4 + CO products, where the former channel is preferable at higher temperatures from 1000 K and above. In the C 2 H 4 + CO product pair, the ethylene molecule can be formed either adiabatically in the triplet electronic state or via triplet‐singlet intersystem crossing in the singlet electronic state occurring in the vicinity of the CH 2 COCH 2 intermediate or along the pathway of CO elimination from the initial CH 2 CH 2 CO complex. The predominant products of the reaction of ketene with singlet methylene have been shown to be C 2 H 4 + CO. The formation of these products mostly proceeds via a well‐skipping mechanism but at high pressures may to some extent involve collisional stabilization of the CH 3 CHCO and cyclic CH 2 COCH 2 intermediates followed by their thermal unimolecular decomposition. The calculated rate constants at different pressures from 0.01 to 100 atm have been fitted by the modified Arrhenius expressions in the temperature range of 300–3000 K, which are proposed for kinetic modeling of ketene reactions in combustion. © 2018 Wiley Periodicals, Inc.