New ab initio potential energy surface for BrH2 and rate constants for the H + HBr → H2 + Br abstraction reaction. 2011

Bin Jiang, and Changjian Xie, and Daiqian Xie
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.

A global potential energy surface (PES) for the electronic ground state of the BrH(2) system was constructed based on the multireference configuration interaction (MRCI) method including the Davidson's correction using a large basis set. In addition, the spin-orbit correction were computed using the Breit-Pauli Hamiltonian and the unperturbed MRCI wavefunctions in the Br + H(2) channel and the transition state region. Adding the correction to the ground state potential, the lowest spin-orbit correlated adiabatic potential was obtained. The characters of the new potential are discussed. Accurate initial state specified rate constants for the H + HBr → H(2) + Br abstraction reaction were calculated using a time-dependent wave packet method. The predicted rate constants were found to be in excellent agreement with the available experimental values and much better than those obtained from a previous PES.

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