Quantum tunneling splittings from path-integral molecular dynamics.
Accepted version
Peer-reviewed
Repository URI
Repository DOI
Change log
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
1089-7690
Volume Title
144
Publisher
AIP Publishing
Publisher DOI
Sponsorship
Engineering and Physical Sciences Research Council (EP/L010518/1)
Engineering and Physical Sciences Research Council (EP/N035003/1)
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.