Non-adiabatic effects in F+CHD3 reactive scattering

JULIANA PALMA; UWE MANTHE

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Lugar: New York; Año: 2017 vol. 146 p. 214117 - 214117

0021-9606

The effect of non-adiabatic transitions on the F(2P)+CHD3 (ν1 ) => DF + CHD2 and F(2P)+CHD3 (ν1) => HF + CD3 reactions is investigated. The dynamics of the nuclei was simulated using trajectory surface hopping and a vibronically and spin-orbit coupled diabatic potential energy matrix. To facilitate the calculations, the fewest switching algorithm of Tully was adapted to the use of a complex diabatic potential energy matrix. For reactions of CHD3 with ground state flourine atoms, F(2P3/2), the ratio between the previously-computed adiabatic cross sections and the non-adiabatic ones was found to range from 1.4 to 2.1. The actual ratio depends on the translational energy and the initial vibrational state of CHD3. The total reactivity of CHD3 (ν1=1) was found to be always larger than that of CHD3(ν1=0), mainly because of the increase in the cross sections for the HF + CD3 channel. Thus, the inclusion of non-adiabatic transitions in the theoretical treatment can not resolve the existing disagreement between theory and experiment. Cross sections for the reaction of CHD3 with spin-orbit excited flourine atoms, F(2P1/2), were found to be significantly smaller than the ones for reaction with F(2P3/2).