Blip decomposition of the path integral: Exponential acceleration of real-time calculations on quantum dissipative systems

被引:63
|
作者
Makri, Nancy [1 ,2 ]
机构
[1] Univ Illinois, Dept Chem, Urbana, IL 61801 USA
[2] Univ Illinois, Dept Phys, Urbana, IL 61801 USA
来源
JOURNAL OF CHEMICAL PHYSICS | 2014年 / 141卷 / 13期
基金
美国国家科学基金会;
关键词
INITIAL-VALUE REPRESENTATION; BACKWARD SEMICLASSICAL DYNAMICS; ELECTRON-TRANSFER REACTIONS; REDUCED DENSITY-MATRICES; DISCRETE VARIABLE REPRESENTATIONS; PHOTOSYNTHETIC REACTION CENTERS; COMPLEX MOLECULAR-SYSTEMS; CHARGE-TRANSFER DYNAMICS; THERMAL RATE CONSTANTS; LIQUID PARA-HYDROGEN;
D O I
10.1063/1.4896736
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
The real-time path integral representation of the reduced density matrix for a discrete system in contact with a dissipative medium is rewritten in terms of the number of blips, i.e., elementary time intervals over which the forward and backward paths are not identical. For a given set of blips, it is shown that the path sum with respect to the coordinates of all remaining time points is isomorphic to that for the wavefunction of a system subject to an external driving term and thus can be summed by an inexpensive iterative procedure. This exact decomposition reduces the number of terms by a factor that increases exponentially with propagation time. Further, under conditions (moderately high temperature and/or dissipation strength) that lead primarily to incoherent dynamics, the "fully incoherent limit" zero-blip term of the series provides a reasonable approximation to the dynamics, and the blip series converges rapidly to the exact result. Retention of only the blips required for satisfactory convergence leads to speedup of full-memory path integral calculations by many orders of magnitude. (C) 2014 AIP Publishing LLC.
引用
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页数:10
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