Extended Lagrangian Excited State Molecular Dynamics
Abstract
In this work, an extended Lagrangian framework for excited state molecular dynamics (XLESMD) using timedependent selfconsistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a timedependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the selfconsistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XLESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as timedependent Hartree–Fock (TDHF), Configuration Interactions Singles (CIS), and timedependent density functional theory (TDDFT).
 Authors:

 Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
 Publication Date:
 Research Org.:
 Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
 Sponsoring Org.:
 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC22); USDOE National Nuclear Security Administration (NNSA)
 OSTI Identifier:
 1422924
 Report Number(s):
 LAUR1727227
Journal ID: ISSN 15499618; TRN: US1801670
 Grant/Contract Number:
 AC5206NA25396
 Resource Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Theory and Computation
 Additional Journal Information:
 Journal Volume: 14; Journal Issue: 2; Journal ID: ISSN 15499618
 Publisher:
 American Chemical Society
 Country of Publication:
 United States
 Language:
 English
 Subject:
 97 MATHEMATICS AND COMPUTING; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; molecular dynamics; density functional theory; extended lagrangian
Citation Formats
Bjorgaard, Josiah August, Sheppard, Daniel Glen, Tretiak, Sergei, and Niklasson, Anders Mauritz. Extended Lagrangian Excited State Molecular Dynamics. United States: N. p., 2018.
Web. doi:10.1021/acs.jctc.7b00857.
Bjorgaard, Josiah August, Sheppard, Daniel Glen, Tretiak, Sergei, & Niklasson, Anders Mauritz. Extended Lagrangian Excited State Molecular Dynamics. United States. doi:10.1021/acs.jctc.7b00857.
Bjorgaard, Josiah August, Sheppard, Daniel Glen, Tretiak, Sergei, and Niklasson, Anders Mauritz. Tue .
"Extended Lagrangian Excited State Molecular Dynamics". United States. doi:10.1021/acs.jctc.7b00857. https://www.osti.gov/servlets/purl/1422924.
@article{osti_1422924,
title = {Extended Lagrangian Excited State Molecular Dynamics},
author = {Bjorgaard, Josiah August and Sheppard, Daniel Glen and Tretiak, Sergei and Niklasson, Anders Mauritz},
abstractNote = {In this work, an extended Lagrangian framework for excited state molecular dynamics (XLESMD) using timedependent selfconsistent field theory is proposed. The formulation is a generalization of the extended Lagrangian formulations for ground state Born–Oppenheimer molecular dynamics [Phys. Rev. Lett. 2008 100, 123004]. The theory is implemented, demonstrated, and evaluated using a timedependent semiempirical model, though it should be generally applicable to ab initio theory. The simulations show enhanced energy stability and a significantly reduced computational cost associated with the iterative solutions of both the ground state and the electronically excited states. Relaxed convergence criteria can therefore be used both for the selfconsistent ground state optimization and for the iterative subspace diagonalization of the random phase approximation matrix used to calculate the excited state transitions. In conclusion, the XLESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as timedependent Hartree–Fock (TDHF), Configuration Interactions Singles (CIS), and timedependent density functional theory (TDDFT).},
doi = {10.1021/acs.jctc.7b00857},
journal = {Journal of Chemical Theory and Computation},
number = 2,
volume = 14,
place = {United States},
year = {2018},
month = {1}
}
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