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

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 paper, 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. Finally, 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:
ORCiD logo [1] ; ORCiD logo [2] ;  [3]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division. Center for Nonlinear Studies
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division. Center for Nonlinear Studies. Center for Integrated Nanotechnologies
Publication Date:
Report Number(s):
LA-UR-16-20658
Journal ID: ISSN 0021-9606
Grant/Contract Number:
AC52-06NA25396
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 15; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Laboratory Directed Research and Development (LDRD) Program
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solvation; excited state; state specific; nonequilibrium; solvents; carrier density; ground states; molecular dynamics
OSTI Identifier:
1338760