Quasiclassical Trajectory Calculations of the Rate Constant of the OH + HBr → Br + H2O Reaction Using a Full-Dimensional Ab Initio Potential Energy Surface Over the Temperature Range 5 to 500 K.
We report a permutationally invariant, ab initio potential energy surface (PES) for the OH + HBr → Br + H2O reaction. The PES is a fit to roughly 26 000 spin-free UCCSD(T)/cc-pVDZ-F12a energies and has no classical barrier to reaction. It is used in quasiclassical trajectory calculations with a focus on the thermal rate constant, k(T), over the temperature range 5 to 500 K. Comparisons with available experimental data over the temperature range 23 to 416 K are made using three approaches to treat the OH rotational and associated electronic partition function. All display an inverse temperature dependence of k(T) below roughly 160 K and a nearly constant temperature dependence above 160 K, in agreement with experiment. The calculated rate constant with no treatment of spin-orbit coupling is overall in the best agreement with experiment, being (probably fortuitously) within 20% of it.
†Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, São Paulo, 05508-000, Brazil.|‡Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Antonio G S
AG
de Oliveira-Filho
†Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, São Paulo, São Paulo, 05508-000, Brazil.
Fernando R
FR
Ornellas
‡Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Joel M
JM
Bowman
ab initio calculations; atmospheric chemistry; chemical kinetics; non-Arrhenius behavior; potential energy surfaces; quasiclassical trajectory calculation; reaction rate constant