A quenching method in mixed quantum-classical dynamics calculations on nonadiabatic problems

被引:11
作者
Wang, LC
机构
[1] Univ London Univ Coll, Dept Chem, London WC1H 0AJ, England
[2] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England
关键词
D O I
10.1063/1.476187
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A quenching method [Chem. Phys. Let. 262, 284 (1996)] is extended to study nonadiabatic reactive scattering within a mixed quantum-classical molecular dynamics simulation based on the time dependent self-consistent field. The quenching method is more straightforward for nonadiabatic reactive scattering than for the adiabatic case. A rigorous diabatic-adiabatic transformation for nonadiabatic problems is presented. It provides a theoretical basis for decoupling the bifurcating wavepacket in adiabatic reactive scattering and a new decoupling technique. The derivation illustrates clearly that a diabatic representation is convenient for both adiabatic and nonadiabatic reactive scattering within the mixed quantum-classical formulation. Two model examples are used to demonstrate the advantages of the quenching method for nonadiabatic reactive scattering. A comparison with the full quantum treatment is also made. (C) 1998 American Institute of Physics.
引用
收藏
页码:7538 / 7548
页数:11
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