Article (Scientific journals)
Modeling quantum nuclei with perturbed path integral molecular dynamics
Poltavsky, Igor; TKATCHENKO, Alexandre
2016In Chemical Science, 7 (2), p. 1368-1372
Peer reviewed
 

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Abstract :
[en] The quantum nature of nuclear motions plays a vital role in the structure, stability, and thermodynamics of molecules and materials. The standard approach to model nuclear quantum fluctuations in chemical and biological systems is to use path-integral molecular dynamics. Unfortunately, conventional path-integral simulations can have an exceedingly large computational cost due to the need to employ an excessive number of coupled classical subsystems (beads) for quantitative accuracy. Here, we combine perturbation theory with the Feynman-Kac imaginary-time path integral approach to quantum mechanics and derive an improved non-empirical partition function and estimators to calculate converged quantum observables. Our perturbed path-integral (PPI) method requires the same ingredients as the conventional approach but increases the accuracy and efficiency of path integral simulations by an order of magnitude. Results are presented for the thermodynamics of fundamental model systems, an empirical water model containing 256 water molecules within periodic boundary conditions, and ab initio simulations of nitrogen and benzene molecules. For all of these examples, PPI simulations with 4 to 8 classical beads recover the nuclear quantum contribution to the total energy and heat capacity at room temperature within a 3 accuracy, paving the way toward seamless modeling of nuclear quantum effects in realistic molecules and materials.
Disciplines :
Chemistry
Author, co-author :
Poltavsky, Igor;  Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany
TKATCHENKO, Alexandre ;  Fritz-Haber-Institut der Max-Planck-Gesellschaft , Faradayweg 4-6, 14195 Berlin, Germany
External co-authors :
yes
Language :
English
Title :
Modeling quantum nuclei with perturbed path integral molecular dynamics
Publication date :
2016
Journal title :
Chemical Science
ISSN :
2041-6520
Publisher :
Royal Society of Chemistry, THOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS ENGLAND, Unknown/unspecified
Volume :
7
Issue :
2
Pages :
1368-1372
Peer reviewed :
Peer reviewed
Commentary :
Article
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since 26 February 2016

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