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Title: Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states

Abstract

The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited state molecular dynamics. In this work, we describe methods of simulating nonequilibrium solvent effects in excited state molecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission.

Authors:
 [1]
  1. Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States)
Publication Date:
OSTI Identifier:
22660834
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 15; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BORN-OPPENHEIMER APPROXIMATION; DEGREES OF FREEDOM; DENSITY FUNCTIONAL METHOD; EXCITED STATES; MOLECULAR DYNAMICS METHOD; PHOTOCHEMICAL REACTIONS; SOLUTES; SOLVENTS; TIME DEPENDENCE

Citation Formats

Bjorgaard, J. A., E-mail: jbjorgaard@lanl.gov, Velizhanin, K. A., and Tretiak, S., E-mail: serg@lanl.gov. Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states. United States: N. p., 2016. Web. doi:10.1063/1.4946009.
Bjorgaard, J. A., E-mail: jbjorgaard@lanl.gov, Velizhanin, K. A., & Tretiak, S., E-mail: serg@lanl.gov. Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states. United States. https://doi.org/10.1063/1.4946009
Bjorgaard, J. A., E-mail: jbjorgaard@lanl.gov, Velizhanin, K. A., and Tretiak, S., E-mail: serg@lanl.gov. 2016. "Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states". United States. https://doi.org/10.1063/1.4946009.
@article{osti_22660834,
title = {Nonequilibrium solvent effects in Born-Oppenheimer molecular dynamics for ground and excited electronic states},
author = {Bjorgaard, J. A., E-mail: jbjorgaard@lanl.gov and Velizhanin, K. A. and Tretiak, S., E-mail: serg@lanl.gov},
abstractNote = {The effects of solvent on molecular processes such as excited state relaxation and photochemical reaction often occurs in a nonequilibrium regime. Dynamic processes such as these can be simulated using excited state molecular dynamics. In this work, we describe methods of simulating nonequilibrium solvent effects in excited state molecular dynamics using linear-response time-dependent density functional theory and apparent surface charge methods. These developments include a propagation method for solvent degrees of freedom and analytical energy gradients for the calculation of forces. Molecular dynamics of acetaldehyde in water or acetonitrile are demonstrated where the solute-solvent system is out of equilibrium due to photoexcitation and emission.},
doi = {10.1063/1.4946009},
url = {https://www.osti.gov/biblio/22660834}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 15,
volume = 144,
place = {United States},
year = {Thu Apr 21 00:00:00 EDT 2016},
month = {Thu Apr 21 00:00:00 EDT 2016}
}