A size-consistent multi-state mapping approach to surface hopping

被引:8
作者
Lawrence, Joseph E. [1 ,2 ,3 ]
Mannouch, Jonathan R. [4 ,5 ]
Richardson, Jeremy O. [1 ]
机构
[1] Swiss Fed Inst Technol, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland
[2] NYU, Simons Ctr Computat Phys Chem, New York, NY 10003 USA
[3] NYU, Dept Chem, New York, NY 10003 USA
[4] Univ Hamburg, Hamburg Ctr Ultrafast Imaging, Luruper Chaussee 149, D-22761 Hamburg, Germany
[5] Max Planck Inst Struct & Dynam Matter, Luruper Chaussee 149, D-22761 Hamburg, Germany
关键词
MOLECULAR-DYNAMICS; SEMICLASSICAL DESCRIPTION; ELECTRONIC-TRANSITIONS; QUANTUM DECOHERENCE; PHASE-SPACE; SCATTERING; SYSTEMS; MODEL; SIMULATION; EXCITATION;
D O I
10.1063/5.0208575
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
We develop a multi-state generalization of the recently proposed mapping approach to surface hopping (MASH) for the simulation of electronically nonadiabatic dynamics. This new approach extends the original MASH method to be able to treat systems with more than two electronic states. It differs from previous approaches in that it is size consistent and rigorously recovers the original two-state MASH in the appropriate limits. We demonstrate the accuracy of the method by applying it to a series of model systems for which exact benchmark results are available, and we find that the method is well suited to the simulation of photochemical relaxation processes.
引用
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页数:18
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