Surface hopping with a manifold of electronic states. I. Incorporating surfaceleaking to capture lifetimes
Abstract
We investigate the incorporation of the surfaceleaking (SL) algorithm into Tully’s fewestswitches 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 SLFSSH algorithm is benchmarked against exact quantum scattering calculations for three onedimensional model problems. The results show excellent agreement between SLFSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SLFSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SLFSSH, 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 nonadiabatic processes cannot ignore shorttime coherence)
 Authors:
 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; ONEDIMENSIONAL CALCULATIONS; POTENTIALS; PROBABILISTIC ESTIMATION; RELAXATION; RELIABILITY; SCATTERING; SURFACES
Citation Formats
Ouyang, Wenjun, Dou, Wenjie, and Subotnik, Joseph E., Email: subotnik@sas.upenn.edu. Surface hopping with a manifold of electronic states. I. Incorporating surfaceleaking to capture lifetimes. United States: N. p., 2015.
Web. doi:10.1063/1.4908032.
Ouyang, Wenjun, Dou, Wenjie, & Subotnik, Joseph E., Email: subotnik@sas.upenn.edu. Surface hopping with a manifold of electronic states. I. Incorporating surfaceleaking to capture lifetimes. United States. doi:10.1063/1.4908032.
Ouyang, Wenjun, Dou, Wenjie, and Subotnik, Joseph E., Email: subotnik@sas.upenn.edu. 2015.
"Surface hopping with a manifold of electronic states. I. Incorporating surfaceleaking to capture lifetimes". United States.
doi:10.1063/1.4908032.
@article{osti_22416165,
title = {Surface hopping with a manifold of electronic states. I. Incorporating surfaceleaking to capture lifetimes},
author = {Ouyang, Wenjun and Dou, Wenjie and Subotnik, Joseph E., Email: subotnik@sas.upenn.edu},
abstractNote = {We investigate the incorporation of the surfaceleaking (SL) algorithm into Tully’s fewestswitches 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 SLFSSH algorithm is benchmarked against exact quantum scattering calculations for three onedimensional model problems. The results show excellent agreement between SLFSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SLFSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SLFSSH, 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 nonadiabatic processes cannot ignore shorttime coherence)},
doi = {10.1063/1.4908032},
journal = {Journal of Chemical Physics},
number = 8,
volume = 142,
place = {United States},
year = 2015,
month = 2
}

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