Iterative blip-summed path integral for quantum dynamics in strongly dissipative environments

被引:40
作者
Makri, Nancy [1 ,2 ]
机构
[1] Univ Illinois, Dept Chem, 1209 W Calif St, Urbana, IL 61801 USA
[2] Univ Illinois, Dept Phys, 1110 W Green St, Urbana, IL 61801 USA
基金
美国国家科学基金会;
关键词
INITIAL-VALUE REPRESENTATION; BACKWARD SEMICLASSICAL DYNAMICS; REDUCED DENSITY-MATRICES; DISCRETE VARIABLE REPRESENTATIONS; ELECTRON-TRANSFER REACTIONS; TIME-CORRELATION FUNCTIONS; COMPLEX MOLECULAR-SYSTEMS; THERMAL RATE CONSTANTS; LIQUID PARA-HYDROGEN; SPIN-BOSON MODELS;
D O I
10.1063/1.4979197
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 iterative decomposition of the blip-summed path integral [N. Makri, J. Chem. Phys. 141, 134117 (2014)] is described. The starting point is the expression of the reduced density matrix for a quantum system interacting with a harmonic dissipative bath in the form of a forward-backward path sum, where the effects of the bath enter through the Feynman-Vernon influence functional. The path sum is evaluated iteratively in time by propagating an array that stores blip configurations within the memory interval. Convergence with respect to the number of blips and the memory length yields numerically exact results which are free of statistical error. In situations of strongly dissipative, sluggish baths, the algorithm leads to a dramatic reduction of computational effort in comparison with iterative path integral methods that do not implement the blip decomposition. This gain in efficiency arises from (i) the rapid convergence of the blip series and (ii) circumventing the explicit enumeration of between-blip path segments, whose number grows exponentially with the memory length. Application to an asymmetric dissipative two-level system illustrates the rapid convergence of the algorithm even when the bath memory is extremely long. Published by AIP Publishing.
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页数:8
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