Global potential energy surfaces for the lowest three doublet states (1A', 2A', and 1A") of the BrH system

Kurosaki, Yuzuru; Takayanagi, Toshiyuki

Journal of Chemical Physics, 119(15), p.7838 - 7856, 2003/10

https://doi.org/10.1063/1.1609398

Adiabatic potential energy surfaces of the lowest three doublet states (1A', 2A', and 1A") for the BrH system have been calculated globally using the MRCI+Q method with the aug-cc-pVTZ basis set. Spin-orbit effects were considered on the basis of Breit-Pauli Hamiltonian. The calculated adiabatic energies were fitted to the analytical functional form of many-body expansion. The barrier heights of the abstraction and exchange reactions on the ground-state PES were calculated to be 1.28 and 11.71 kcal mol, respectively, at the MRCI+Q/aug-cc-pVTZ level of theory. The fits for the three PESs were successful within the accuracy of 0.1 kcal mol. Thermal rate constants for the abstraction and exchange reactions and their isotopic variants were calculated with the fitted 1A' PES using the ICVT/LAG method. The calculated rate constants for the abstarction reactions agree fairly well with experiment but those for the exchange reactions were much smaller than experiment, which suggests that the reliable experimental data are still insufficient.