Tunneling Splittings in Water Clusters from Path Integral Molecular Dynamics.
The journal of physical chemistry letters
American Chemical Society
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Vaillant, C. L. J. J., Wales, D., & Althorpe, S. (2019). Tunneling Splittings in Water Clusters from Path Integral Molecular Dynamics.. The journal of physical chemistry letters, 10 (22), 7300-7304. https://doi.org/10.1021/acs.jpclett.9b02951
We present calculations of tunneling splittings in selected small water clusters, based on a recently-developed path integral molecular dynamics (PIMD) method. The ground- rotational-state tunneling motions associated with the largest splittings in the water dimer, trimer, and hexamer are considered, and we show that the PIMD predictions are in very good agreement with benchmark quantum and experimental results. As the tunneling spectra are highly sensitive to both the details of the quantum dynamics and the potential energy surface, our calculations are a validation of the MB-Pol surface as well as the accuracy of PIMD. The favourable scaling of PIMD with system size paves the way for calculations of tunneling splittings in large, non-rigid molecular systems with motions that cannot be treated accurately by other methods, such as the semi- classical instanton.
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External DOI: https://doi.org/10.1021/acs.jpclett.9b02951
This record's URL: https://www.repository.cam.ac.uk/handle/1810/299089
Attribution 4.0 International
Licence URL: https://creativecommons.org/licenses/by/4.0/