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Mechanistic and kinetics study on the reaction of CF 3 CBrCH 2 with OH: A theoretical study
Author(s) -
Zhang Yunju,
Sun Yuxi
Publication year - 2020
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.4079
Subject(s) - chemistry , reaction rate constant , kinetics , adduct , dissociation (chemistry) , torr , computational chemistry , thermodynamics , organic chemistry , quantum mechanics , physics
Quantum chemical method (CCSD(T)/cc‐pVTZ//M06‐2X/6‐311++G(d,p)) is employed to research the CF 3 CBrCH 2 + OH reaction. The results indicate that the reaction takes place through the interaction of the oxygen atom of the OH radical with the middle C and terminal C atom of CF 3 CBrCH 2 generating adduct IM1 (CF 3 CBrCH 2 OH) and IM2 (CF 3 CBrOHCH 2 ), respectively, and then further dissociation or rearrangement to many products. The rate constants have been computed at 10 −10 to 10 10 Torr and 200–3000 K by RRKM theory for various product pathways. The results show that at 200–800 K, the rate constant for the production of IM1 (CF 3 CBrCH 2 OH) by collisional deactivation is dominant; at high temperatures, the production of P1 (CF 3 CBrCHOH + H) becomes predominate. The predicted data for CF 3 CBrCH 2 + OH agree closely with available experimental value. The total rate constants are independent on pressure and dependent on temperature. The rate equation can be fitted as k ( T ) = 1.77 × 10 −7 T −0.65 exp(−4518.77/ T ) at 200–300 K, 30 Torr of Ar. The atmospheric lifetime of CF 3 CBrCH 2 in OH is around 2.77 days. TD‐DFT computations imply that IM1, IM2, IM3, IM4, IM5, and IM6 will photolyze under the sunlight.