Abstract
The diversity of the various forms of water stems from systems of hydrogen bonds. Cooperative behaviour of hydrogen-bond networks gives rise to unique properties of water systems. A number of approaches to understand and model the collective behaviour of hydrogen bonds and predict their properties on the basis of a small number of calculations have been put forward. Among them, the concept of graph invariants provides most general descriptors for hydrogen-bond networks, which are routinely used to predict properties of water systems. In the present work, we examine the formalism of graph invariants and propose its modification which may be beneficial for water structures with defects. To benchmark graph invariants, we carried out quantum-chemical calculations of more than \(10^7\) water clusters with different hydrogen-bond configurations. The quality of the approximation is studied as a function of the type of graph invariant and its order. The results demonstrate that the method is applicable only to cage-like structures without significant strains.
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Acknowledgments
This work is partially supported by National Research Center “Kurchatov Institute”, Russian Science Foundation (Grant 14-19-00662), and Russian Foundation for Basic Research (Grants 13-07-00095 and 14-03-00867).
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Published as part of the special collection of articles “Festschrift in honour of P. R. Surjan”.
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Tokmachev, A.M., Tchougréeff, A.L. & Dronskowski, R. Benchmarks of graph invariants for hydrogen-bond networks in water clusters of different topology. Theor Chem Acc 134, 115 (2015). https://doi.org/10.1007/s00214-015-1720-9
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DOI: https://doi.org/10.1007/s00214-015-1720-9