TY - JOUR
T1 - A quantum wave-packet study of intersystem crossing effects in the O (P 2,1,0 3, D21) + H2 reaction
AU - Chu, Tian Shu
AU - Zhang, Xin
AU - Han, Ke Li
N1 - Funding Information:
This work was supported by NKBRSF (Contract No. 1999075302), the Knowledge Innovation Program of the Chinese Academy of Sciences (Contract No. INF105-SCE-02-08), and NSFC (Contract Nos. 20373071 and 20333050). The authors thank Aron Kuppermann and George Schatz for providing the PESs and the spin–orbit matrix used in this study.
PY - 2005/6/1
Y1 - 2005/6/1
N2 - 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 A′1 state [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)], the A′3 and the two degenerate A″3 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 Π32 to Π12 of the product OH was calculated to be ∼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.
AB - 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 A′1 state [J. Dobbyn and P. J. Knowles, Faraday Discuss. 110, 247 (1998)], the A′3 and the two degenerate A″3 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 Π32 to Π12 of the product OH was calculated to be ∼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.
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U2 - 10.1063/1.1924507
DO - 10.1063/1.1924507
M3 - Article
C2 - 15974732
AN - SCOPUS:21244462345
SN - 0021-9606
VL - 122
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 21
M1 - 214301
ER -