Quantum tunneling splittings from path-integral molecular dynamics

E. Mat́yus, David J. Wales, Stuart C. Althorpe

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.

Original languageEnglish
Article number114108
JournalThe Journal of Chemical Physics
Volume144
Issue number11
DOIs
Publication statusPublished - Mar 21 2016

Fingerprint

Malondialdehyde
Ground state
Molecular dynamics
Thermodynamics
molecular dynamics
Molecules
thermodynamics
ground state
molecules

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Quantum tunneling splittings from path-integral molecular dynamics. / Mat́yus, E.; Wales, David J.; Althorpe, Stuart C.

In: The Journal of Chemical Physics, Vol. 144, No. 11, 114108, 21.03.2016.

Research output: Contribution to journalArticle

Mat́yus, E. ; Wales, David J. ; Althorpe, Stuart C. / Quantum tunneling splittings from path-integral molecular dynamics. In: The Journal of Chemical Physics. 2016 ; Vol. 144, No. 11.
@article{df15c72dc1484239ba48c376966e6fc7,
title = "Quantum tunneling splittings from path-integral molecular dynamics",
abstract = "We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.",
author = "E. Mat́yus and Wales, {David J.} and Althorpe, {Stuart C.}",
year = "2016",
month = "3",
day = "21",
doi = "10.1063/1.4943867",
language = "English",
volume = "144",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "11",

}

TY - JOUR

T1 - Quantum tunneling splittings from path-integral molecular dynamics

AU - Mat́yus, E.

AU - Wales, David J.

AU - Althorpe, Stuart C.

PY - 2016/3/21

Y1 - 2016/3/21

N2 - We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.

AB - We illustrate how path-integral molecular dynamics can be used to calculate ground-state tunnelling splittings in molecules or clusters. The method obtains the splittings from ratios of density matrix elements between the degenerate wells connected by the tunnelling. We propose a simple thermodynamic integration scheme for evaluating these elements. Numerical tests on fully dimensional malonaldehyde yield tunnelling splittings in good overall agreement with the results of diffusion Monte Carlo calculations.

UR - http://www.scopus.com/inward/record.url?scp=84961615236&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84961615236&partnerID=8YFLogxK

U2 - 10.1063/1.4943867

DO - 10.1063/1.4943867

M3 - Article

VL - 144

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 11

M1 - 114108

ER -