Dual-level direct dynamics studies for the reactions of OH radical with bromine-substituted ethanes

• Published in: Journal of computational chemistry 2009-03, Vol.30 (4), p.611-620
• Main Authors: Wang, Li, Liu, Jing-yao, Gao, Hong, Wan, Su-qin, Li, Ze-sheng
• Format: Article
• Language: English
• Subjects: Bromates; Chemical reactions; direct dynamics; Fuels; Hydrogen; Methods; rate constant; variational transition-state theory
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.21093

The dynamic properties of the multichannel hydrogen abstraction reactions of CH₃CH₂Br + OH [rightward arrow] products and CH₃CHBr₂ + OH [rightward arrow] products are studied by dual-level direct dynamics method. For each reaction, three reaction channels, one for α-hydrogen abstraction and two for β-hydrogen abstractions, have been identified. The minimum energy paths (MEPs) of both the reactions are calculated at the Becke's half-and-half (BH&H)-Lee-Yang-Parr (LYP)/6-311G(d, p) level and the energy profiles along the MEPs are further refined with interpolated single-point energies (ISPE) method at the G2M(RCC5)//BH&H-LYP level. There are complexes with energies less than those of the reactants or products located at the entrance or exit channels, which indicates that the reactions may proceed via an indirect mechanism. By canonical variational transition-state theory (CVT) the rate constants are calculated incorporating the small-curvature tunneling (SCT) correction in the temperature range of 220-2000 K. The agreement of the rate constants with available experimental values for two reactions is good in the measured temperature range. The calculated results show that α-hydrogen abstraction channel is the major reaction pathway in the lower temperature for two reactions, while the contribution of β-hydrogen abstraction will increase with the increase in temperature.