A quantum time-dependent wave-packet study of intersystem crossing effects in the O(3P0, 1, 2) + D2(v = 0, j = 0) reaction

Abstract

We investigated spin-orbit-induced intersystem crossing effects in the title reaction by the time-dependent wave-packet method combined with an extended split operator scheme. We performed non-adiabatic calculations of the fine-structure-resolved cross section and adiabatic calculations of integral cross section. The calculations are based on the potential energy surfaces of (3)A(') and the two degenerate (3)A('') states [S. Rogers, D. Wang, A. Kuppermann, and S. Walch, J. Phys. Chem. A 104, 2308 (2000)], together with the spin-orbit coupling matrix [B. Maiti and G. C. Schatz, J. Chem. Phys. 119, 12360 (2003)] and singlet (1)A(') potential energy surface [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)]. The results of the O((3)P) + D2 are similar to those of the O((3)P) + H2 reaction. The product spin state-resolved reaction cross section and the total reaction cross section both show that the adiabatic channel is dominant in all cases, and the non-adiabatic channels have cross sections of several orders of magnitude smaller than the adiabatic channels at high collision energy. Although the cross sections caused by the intersystem crossing effects in the O((3)P) + D2 reaction are larger than those in the O((3)P) + H2 reaction, the differences in non-adiabaticity between these two reaction systems are quite modest. Based on the results of the O((3)P) + H2 reaction, we can predict that the influence of spin-orbit on the total reaction cross sections of the O((3)P) + D2 reaction is also insignificant. However, these non-adiabatic effects can be reflected in the presence of some forward-scattering in the angular distribution for the OD product.