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Volume 195, 2016
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Blip-summed quantum–classical path integral with cumulative quantum memory

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Abstract

The quantum-classical path integral (QCPI) offers a rigorous methodology for simulating quantum mechanical processes in condensed-phase environments treated in full atomistic detail. This paper describes the implementation of QCPI on system–bath models, which are frequently employed in studying the dynamics of reactive processes. The QCPI methodology incorporates all effects associated with stimulated phonon absorption and emission as its crudest limit, thus can (in some regimes) converge faster than influence functional-based path integral methods specifically designed for system–bath Hamiltonians. It is shown that the QCPI phase arising from a harmonic bath can be summed analytically with respect to the discrete bath degrees of freedom and expressed in terms of precomputed influence functional coefficients, avoiding the explicit enumeration of forced oscillator trajectories, whose number grows exponentially with the length of quantum memory. Further, adoption of the blip decomposition (which classifies the system paths based on the time length over which their forward and backward components are not identical) and a cumulative treatment of the QCPI phase between blips allows elimination of the majority of system paths, leading to a dramatic increase in efficiency. The generalization of these acceleration techniques to anharmonic environments is discussed.

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Article information


Submitted
31 May 2016
Accepted
07 Jul 2016
First published
19 Oct 2016

Faraday Discuss., 2016,195, 81-92
Article type
Paper

Blip-summed quantum–classical path integral with cumulative quantum memory

N. Makri, Faraday Discuss., 2016, 195, 81 DOI: 10.1039/C6FD00142D

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