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Title: Solvent effects in time-dependent self-consistent field methods. II. Variational formulations and analytical gradients

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4927167· OSTI ID:1236703
ORCiD logo [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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This study describes variational energy expressions and analytical excited state energy gradients for time-dependent self-consistent field methods with polarizable solvent effects. Linear response, vertical excitation, and state-specific solventmodels are examined. Enforcing a variational ground stateenergy expression in the state-specific model is found to reduce it to the vertical excitation model. Variational excited state energy expressions are then provided for the linear response and vertical excitation models and analytical gradients are formulated. Using semiempiricalmodel chemistry, the variational expressions are verified by numerical and analytical differentiation with respect to a static external electric field. Lastly, analytical gradients are further tested by performing microcanonical excited state molecular dynamics with p-nitroaniline.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC52-06NA25396
OSTI ID:
1236703
Alternate ID(s):
OSTI ID: 1229576
Report Number(s):
LA-UR-15-21181; JCPSA6; TRN: US1600390
Journal Information:
Journal of Chemical Physics, Vol. 143, Issue 5; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
solvents
ground states
excitation energies
free energy
Lagrangian mechanics