Quantum tunnelling pathways of the water pentamer

We apply the semiclassical instanton method to calculate all feasible tunnelling pathways in the water pentamer. Similarly to the water trimer, there are labile flip dynamics as well as a number of different bifurcation pathways coupled to flips. In contrast to the trimer, the puckering motion of th...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2020-01, Vol.22 (3), p.135-144
Main Authors: Cvitaš, Marko T, Richardson, Jeremy O
Format: Article
Language:English
Subjects:
Bifurcations
Hydrogen bonding
Instantons
Quantum tunnelling
Trimers
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Summary:We apply the semiclassical instanton method to calculate all feasible tunnelling pathways in the water pentamer. Similarly to the water trimer, there are labile flip dynamics as well as a number of different bifurcation pathways coupled to flips. In contrast to the trimer, the puckering motion of the oxygen ring makes the ring-polymer instanton approach difficult to converge, a problem which is resolved by using a recently developed time-independent formalism of the method. We use the results to predict the complete ground-state tunnelling splitting pattern of 320 states, which should help in the continuing effort to assign the experimental spectrum. A comparison between the rearrangement pathways in the water trimer and pentamer sheds light on the many-body cooperative effects of hydrogen bonding which are important for a full understanding of the liquid state. Five tunnelling rearrangement pathways in water pentamer are responsible for the ground-state tunnelling splitting pattern of 320 states.
ISSN:1463-9076
1463-9084
DOI:10.1039/c9cp05561d