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Title: Extended Lagrangian Excited State Molecular Dynamics

Abstract

In this work, an extended Lagrangian framework for excited state molecular dynamics (XL-ESMD) using time-dependent self-consistent 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 time-dependent 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 self-consistent 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 XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).

Authors:
 [1];  [1];  [1];  [1]
  1. 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) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1422924
Report Number(s):
LA-UR-17-27227
Journal ID: ISSN 1549-9618; TRN: US1801670
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 2; Journal ID: ISSN 1549-9618
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 (XL-ESMD) using time-dependent self-consistent 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 time-dependent 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 self-consistent 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 XL-ESMD approach is expected to enable numerically efficient excited state molecular dynamics for such methods as time-dependent Hartree–Fock (TD-HF), Configuration Interactions Singles (CIS), and time-dependent density functional theory (TD-DFT).},
doi = {10.1021/acs.jctc.7b00857},
journal = {Journal of Chemical Theory and Computation},
issn = {1549-9618},
number = 2,
volume = 14,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

Figure 1 Figure 1: Total energy fluctuations during dynamics on the ground electronic state potential energy surface of acetaldehyde at T≈300K. BOMD are performed using conventional SCF calculations converged to 10−8 eV (denoted with $N_{scf}$ =∞). Notably, a conventional BOMD calculation with $N_{scf}$ = 2 diverges more rapidly than can be displayedmore » on this plot. XLBOMD is performed using 0 or 2 SCF cycles. 0-SCF XL-BOMD demonstrates much less divergence compared to a fully conventional BOMD calculation.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.