Thermodynamics and the potential energy landscape: case study of small water clusters

Dorrell, J. and Partay, L. B. (2019) Thermodynamics and the potential energy landscape: case study of small water clusters. Physical Chemistry Chemical Physics, 21. pp. 7305-7312. ISSN 1463-9076 doi: 10.1039/C9CP00474B

Abstract/Summary

We investigated the structure and the thermodynamic properties of small water clusters with the nested sampling computational technique, using two different water models, the coarse-grained mW (up to 25 molecules) and the flexible version of the TIP3P (up to 16 molecules). With mapping the entire potential energy landscape of the clusters, we calculated the heat capacity curves, located the structural transitions and identified those local minima basins which contribute the most to the total partition function. We found that in case of the mW model, trends in first-order-like and continuous-like transitions can be very well matched to the characteristics of the landscape: cluster sizes with fewer and narrower local minima basins show a sharper ’melting’ peak on the heat capacity curve. Trends in case of the TIP3P model were not easily assigned to changing occupation of basins, and the contribution of local minima were negligible, except for n = 7, 15 and 16.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/82661
Identification Number/DOI	10.1039/C9CP00474B
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Publisher	Royal Society of Chemistry
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