Nonadiabatic Car-Parrinello molecular dynamics

被引:213
作者
Doltsinis, NL [1 ]
Marx, D [1 ]
机构
[1] Ruhr Univ Bochum, Lehrstuhl Theoret Chem, D-44780 Bochum, Germany
关键词
D O I
10.1103/PhysRevLett.88.166402
中图分类号
O4 [物理学];
学科分类号
0702 ;
摘要
An extension of Car-Parrinello (CP) molecular dynamics for efficient treatment of electronically nonadiabatic processes is presented. The current approach couples the S-1 restricted open-shell Kohn-Sham excited state to the S-0 ground state using a surface hopping scheme. Efficient evaluation of the nonadiabatic couplings is achieved by exploiting the available wave function time derivatives. Since the computational cost scales linearly with the number of excited states, the technique makes possible nonadiabatic ab initio simulations of systems of similar complexity to those typically studied by standard CP methods. It is thus ideally suited to study the photochemistry of large molecules, particularly in condensed phases.
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