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Title: An 'optimal' spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics

Abstract

The full multiple spawning (FMS) method has been developed to simulate quantum dynamics in the multistate electronic problem. In FMS, the nuclear wave function is represented in a basis of coupled, frozen Gaussians, and a 'spawning' procedure prescribes a means of adaptively increasing the size of this basis in order to capture population transfer between electronic states. Herein we detail a new algorithm for specifying the initial conditions of newly spawned basis functions that minimizes the number of spawned basis functions needed for convergence. 'Optimally' spawned basis functions are placed to maximize the coupling between parent and child trajectories at the point of spawning. The method is tested with a two-state, one-mode avoided crossing model and a two-state, two-mode conical intersection model.

Authors:
; ; ;  [1]
  1. Department of Chemistry and Beckman Institute, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801 (United States)
Publication Date:
OSTI Identifier:
21255548
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 130; Journal Issue: 13; Other Information: DOI: 10.1063/1.3103930; (c) 2009 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ALGORITHMS; CONVERGENCE; COUPLING; ENERGY LEVELS; EXPANSION; MOLECULAR DYNAMICS METHOD; PHOTOCHEMISTRY; REACTION KINETICS; SURFACES; TRAJECTORIES; WAVE FUNCTIONS

Citation Formats

Yang, Sandy, Coe, Joshua D, Kaduk, Benjamin, and Martinez, Todd J. An 'optimal' spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics. United States: N. p., 2009. Web. doi:10.1063/1.3103930.
Yang, Sandy, Coe, Joshua D, Kaduk, Benjamin, & Martinez, Todd J. An 'optimal' spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics. United States. https://doi.org/10.1063/1.3103930
Yang, Sandy, Coe, Joshua D, Kaduk, Benjamin, and Martinez, Todd J. 2009. "An 'optimal' spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics". United States. https://doi.org/10.1063/1.3103930.
@article{osti_21255548,
title = {An 'optimal' spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics},
author = {Yang, Sandy and Coe, Joshua D and Kaduk, Benjamin and Martinez, Todd J},
abstractNote = {The full multiple spawning (FMS) method has been developed to simulate quantum dynamics in the multistate electronic problem. In FMS, the nuclear wave function is represented in a basis of coupled, frozen Gaussians, and a 'spawning' procedure prescribes a means of adaptively increasing the size of this basis in order to capture population transfer between electronic states. Herein we detail a new algorithm for specifying the initial conditions of newly spawned basis functions that minimizes the number of spawned basis functions needed for convergence. 'Optimally' spawned basis functions are placed to maximize the coupling between parent and child trajectories at the point of spawning. The method is tested with a two-state, one-mode avoided crossing model and a two-state, two-mode conical intersection model.},
doi = {10.1063/1.3103930},
url = {https://www.osti.gov/biblio/21255548}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 13,
volume = 130,
place = {United States},
year = {Tue Apr 07 00:00:00 EDT 2009},
month = {Tue Apr 07 00:00:00 EDT 2009}
}