Understanding the Surface Hopping View of Electronic Transitions and Decoherence

被引:330
作者
Subotnik, Joseph E. [1 ]
Jain, Amber [1 ]
Landry, Brian [1 ]
Petit, Andrew [1 ]
Ouyang, Wenjun [1 ]
Bellonzi, Nicole [1 ]
机构
[1] Univ Penn, Dept Chem, Philadelphia, PA 19104 USA
来源
ANNUAL REVIEW OF PHYSICAL CHEMISTRY, VOL 67 | 2016年 / 67卷
关键词
nonadiabatic dynamics; measurement; electron transfer; energy transfer; INITIO MOLECULAR-DYNAMICS; REDUCED DENSITY-MATRICES; QUANTUM TIME EVOLUTION; NONADIABATIC DYNAMICS; PROTON-TRANSFER; CONICAL INTERSECTIONS; DERIVATIVE COUPLINGS; TENSOR PROPAGATOR; CONDENSED MATTER; EXCITED-STATES;
D O I
10.1146/annurev-physchem-040215-112245
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 present a current, up-to-date review of the surface hopping methodology for solving nonadiabatic problems, 25 years after Tully published the fewest switches surface hopping algorithm. After reviewing the original motivation for and failures of the algorithm, we give a detailed examination of modern advances, focusing on both theoretical and practical issues. We highlight how one can partially derive surface hopping from the Schrodinger equation in the adiabatic basis, how one can change basis within the surface hopping algorithm, and how one should understand and apply the notions of decoherence and wavepacket bifurcation. The question of time reversibility and detailed balance is also examined at length. Recent applications to photoexcited conjugated polymers are discussed briefly.
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页码:387 / 417
页数:31
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