Non-adiabatic molecular dynamics with complex quantum trajectories. I. The diabatic representation.
J Chem Phys
; 137(22): 22A517, 2012 Dec 14.
Article
em En
| MEDLINE
| ID: mdl-23249054
ABSTRACT
We extend a recently developed quantum trajectory method [Y. Goldfarb, I. Degani, and D. J. Tannor, J. Chem. Phys. 125, 231103 (2006)] to treat non-adiabatic transitions. Each trajectory evolves on a single surface according to Newton's laws with complex positions and momenta. The transfer of amplitude between surfaces stems naturally from the equations of motion, without the need for surface hopping. In this paper we derive the equations of motion and show results in the diabatic representation, which is rarely used in trajectory methods for calculating non-adiabatic dynamics. We apply our method to the first two benchmark models introduced by Tully [J. Chem. Phys. 93, 1061 (1990)]. Besides giving the probability branching ratios between the surfaces, the method also allows the reconstruction of the time-dependent wavepacket. Our results are in quantitative agreement with converged quantum mechanical calculations.
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01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Chem Phys
Ano de publicação:
2012
Tipo de documento:
Article
País de afiliação:
Israel