A quantum wave-packet study of intersystem crossing effects in the O(3P2,1,0,1D2)+H2 reaction.
We present for the first time an exact quantum study of spin-orbit-induced intersystem crossing effects in the title reaction. The time-dependent wave-packet method, combined with an extended split operator scheme, is used to calculate the fine-structure resolved cross section. The calculation involves four electronic potential-energy surfaces of the 1A' state [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)], the 3A' and the two degenerate 3A" states [S. Rogers, D. Wang, A. Kuppermann, and S. Wald, J. Phys. Chem. A 104, 2308 (2000)], and the spin-orbit couplings between them [B. Maiti, and G. C. Schatz, J. Chem. Phys. 119, 12360 (2003)]. Our quantum dynamics calculations clearly demonstrate that the spin-orbit coupling between the triplet states of different symmetries has the greatest contribution to the intersystem crossing, whereas the singlet-triplet coupling is not an important effect. A branch ratio of the spin state Pi32 to Pi12 of the product OH was calculated to be approximately 2.75, with collision energy higher than 0.6 eV, when the wave packet was initially on the triplet surfaces. The quantum calculation agrees quantitatively with the previous quasiclassical trajectory surface hopping study.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Tian-Shu
TS
Chu
Xin
X
Zhang
Ke-Li
KL
Han