Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory
Iterative energy minimization with the aim of achieving selfconsistency is a common feature of BornOppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the selfconsistency procedure can be reduced by reusing converged solutions from previous time steps. However, this must be done carefully, as not to break timereversal symmetry, which negatively impacts energy conservation. Selfconsistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities are treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes—in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linearscaling density functional theory (LSDFT) approach. Furthermore, both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LSDFT regimes.
 Authors:

^{[1]};
^{[2]};
^{[3]};
^{[4]}
;
^{[5]};
^{[1]}
 Univ. of Southampton, Southampton (United Kingdom)
 Univ. of Southampton, Southampton (United Kingdom); Gdansk Univ. of Technology, Gdansk (Poland)
 Univ. of California, Berkeley, CA (United States)
 Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
 Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
 Publication Date:
 Report Number(s):
 LAUR1720731
Journal ID: ISSN 00219606; TRN: US1800661
 Grant/Contract Number:
 AC5206NA25396; AC0205CH11231
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 146; Journal Issue: 12; Journal ID: ISSN 00219606
 Publisher:
 American Institute of Physics (AIP)
 Research Org:
 Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
 Sponsoring Org:
 USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC22); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC22)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Computer Science; Mathematics; Material Science; molecular dynamics; polarizable force fields; density functional theory
 OSTI Identifier:
 1414137
 Alternate Identifier(s):
 OSTI ID: 1476472
Vitale, Valerio, Dziedzic, Jacek, Albaugh, Alex, Niklasson, Anders M. N., HeadGordon, Teresa, and Skylaris, Chris Kriton. Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory. United States: N. p.,
Web. doi:10.1063/1.4978684.
Vitale, Valerio, Dziedzic, Jacek, Albaugh, Alex, Niklasson, Anders M. N., HeadGordon, Teresa, & Skylaris, Chris Kriton. Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory. United States. doi:10.1063/1.4978684.
Vitale, Valerio, Dziedzic, Jacek, Albaugh, Alex, Niklasson, Anders M. N., HeadGordon, Teresa, and Skylaris, Chris Kriton. 2017.
"Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory". United States.
doi:10.1063/1.4978684. https://www.osti.gov/servlets/purl/1414137.
@article{osti_1414137,
title = {Performance of extended Lagrangian schemes for molecular dynamics simulations with classical polarizable force fields and density functional theory},
author = {Vitale, Valerio and Dziedzic, Jacek and Albaugh, Alex and Niklasson, Anders M. N. and HeadGordon, Teresa and Skylaris, Chris Kriton},
abstractNote = {Iterative energy minimization with the aim of achieving selfconsistency is a common feature of BornOppenheimer molecular dynamics (BOMD) and classical molecular dynamics with polarizable force fields. In the former, the electronic degrees of freedom are optimized, while the latter often involves an iterative determination of induced point dipoles. The computational effort of the selfconsistency procedure can be reduced by reusing converged solutions from previous time steps. However, this must be done carefully, as not to break timereversal symmetry, which negatively impacts energy conservation. Selfconsistent schemes based on the extended Lagrangian formalism, where the initial guesses for the optimized quantities are treated as auxiliary degrees of freedom, constitute one elegant solution. We report on the performance of two integration schemes with the same underlying extended Lagrangian structure, which we both employ in two radically distinct regimes—in classical molecular dynamics simulations with the AMOEBA polarizable force field and in BOMD simulations with the Onetep linearscaling density functional theory (LSDFT) approach. Furthermore, both integration schemes are found to offer significant improvements over the standard (unpropagated) molecular dynamics formulation in both the classical and LSDFT regimes.},
doi = {10.1063/1.4978684},
journal = {Journal of Chemical Physics},
number = 12,
volume = 146,
place = {United States},
year = {2017},
month = {3}
}
Works referenced in this record:
Semiempirical GGAtype density functional constructed with a longrange dispersion correction
journal, January 2006
journal, January 2006
 Grimme, Stefan
 Journal of Computational Chemistry, Vol. 27, Issue 15, p. 17871799