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Quantum tunneling splittings from path-integral molecular dynamics.

Accepted version
Peer-reviewed

Repository DOI


Type

Article

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Authors

Mátyus, Edit 
Wales, David J 
Althorpe, Stuart C 

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.

Description

Keywords

0307 Theoretical and Computational Chemistry

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

144

Publisher

AIP Publishing
Sponsorship
Engineering and Physical Sciences Research Council (EP/L010518/1)
Engineering and Physical Sciences Research Council (EP/N035003/1)
E.M., D.J.W., and S.C.A. acknowledge funding from the UK Engineering and Physical Sciences Research Council.