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Title: Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes

Abstract

We investigate the incorporation of the surface-leaking (SL) algorithm into Tully’s fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence)

Authors:
; ;  [1]
  1. Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States)
Publication Date:
OSTI Identifier:
22416165
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 8; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ADIABATIC PROCESSES; ALGORITHMS; APPROXIMATIONS; BENCHMARKS; CAPTURE; IMPLEMENTATION; LIFETIME; ONE-DIMENSIONAL CALCULATIONS; POTENTIALS; PROBABILISTIC ESTIMATION; RELAXATION; RELIABILITY; SCATTERING; SURFACES

Citation Formats

Ouyang, Wenjun, Dou, Wenjie, and Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu. Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes. United States: N. p., 2015. Web. doi:10.1063/1.4908032.
Ouyang, Wenjun, Dou, Wenjie, & Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu. Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes. United States. doi:10.1063/1.4908032.
Ouyang, Wenjun, Dou, Wenjie, and Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu. Sat . "Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes". United States. doi:10.1063/1.4908032.
@article{osti_22416165,
title = {Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes},
author = {Ouyang, Wenjun and Dou, Wenjie and Subotnik, Joseph E., E-mail: subotnik@sas.upenn.edu},
abstractNote = {We investigate the incorporation of the surface-leaking (SL) algorithm into Tully’s fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence)},
doi = {10.1063/1.4908032},
journal = {Journal of Chemical Physics},
number = 8,
volume = 142,
place = {United States},
year = {Sat Feb 28 00:00:00 EST 2015},
month = {Sat Feb 28 00:00:00 EST 2015}
}