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Tunneling Splittings in Water Clusters from Path Integral Molecular Dynamics.

Published version
Peer-reviewed

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Abstract

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 favorable scaling of PIMD with system size paves the way for calculations of tunneling splittings in large, nonrigid molecular systems with motions that cannot be treated accurately by other methods, such as the semiclassical instanton.

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Keywords

51 Physical Sciences, 34 Chemical Sciences, 5102 Atomic, Molecular and Optical Physics, 3406 Physical Chemistry

Journal Title

J Phys Chem Lett

Conference Name

Journal ISSN

1948-7185
1948-7185

Volume Title

10

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/L010518/1)
Engineering and Physical Sciences Research Council (EP/N035003/1)