Quantum tunneling splittings from path-integral molecular dynamics

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

Research output: Contribution to journalArticle

15 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

ASJC Scopus subject areas

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

Cite this