Quantum tunneling splittings from path-integral molecular dynamics
The Journal of Chemical Physics
American Institute of Physics
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Mátyus, E., Wales, D., & Althorpe, S. (2016). Quantum tunneling splittings from path-integral molecular dynamics. The Journal of Chemical Physics, 144 (114108)https://doi.org/10.1063/1.4943867
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.
E.M., D.J.W., and S.C.A. acknowledge funding from the UK Engineering and Physical Sciences Research Council.
External DOI: https://doi.org/10.1063/1.4943867
This record's URL: https://www.repository.cam.ac.uk/handle/1810/254592
Attribution-NonCommercial 2.0 UK: England & Wales
Licence URL: http://creativecommons.org/licenses/by-nc/2.0/uk/
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