O formato da água: a estrutura e ligação de hidrogênio nos limites da estabilidade da água líquida

sábado, junho 02, 2018

Structure and hydrogen bonding at the limits of liquid water stability

Flaviu Cipcigan, Vlad Sokhan, Glenn Martyna & Jason Crain

Scientific Reports volume 8, Article number: 1718 (2018) | Download Citation

How water molecules are arranged in the liquid around a central reference molecule. The white areas show high-density "shells" while the orange area shows regions where no water molecules can reside.


Liquid water exhibits unconventional behaviour across its wide range of stability – from its unusually high liquid-vapour critical point down to its melting point and below where it reaches a density maximum and exhibits negative thermal expansion allowing ice to float. Understanding the molecular underpinnings of these anomalies presents a challenge motivating the study of water for well over a century. Here we examine the molecular structure of liquid water across its range of stability, from mild supercooling to the negative pressure and high temperature regimes. We use a recently-developed, electronically-responsive model of water, constructed from gas-phase molecular properties and incorporating many-body, long-range interactions to all orders; as a result the model has been shown to have high transferability from ice to the supercritical regime. We report a link between the anomalous thermal expansion of water and the behaviour of its second coordination shell and an anomaly in hydrogen bonding, which persists throughout liquid water’s range of stability – from the high temperature limit of liquid water to its supercooled regime.


This work was supported by the NPL Strategic Research programme and the STFC Hartree Centre’s Innovation Return on Research programme. FSC acknowledges the Scottish Doctoral Training Centre in Condensed Matter Physics, the NPL Postgraduate Institute and EPSRC for funding under an Industrial CASE studentship. We acknowledge use of Hartree Centre, EPCC and NPL computational resources.

Author information


IBM Research UK, Hartree Centre, Daresbury, WA4 4AD, United Kingdom

Flaviu Cipcigan & Jason Crain

STFC Daresbury Laboratory, Daresbury, WA4 4AD, United Kingdom

Vlad Sokhan

IBM T. J. Watson Research Center, Yorktown Heights, New York, 10598, USA

Glenn Martyna


F.S.C., V.P.S., G.J.M., J.C. designed research. F.S.C., V.P.S. conducted research. F.S.C., V.P.S., G.J.M., J.C. analysed and interpreted the results. All authors reviewed the manuscript.

Competing Interests

The authors declare that they have no competing interests.

Corresponding author

Correspondence to Flaviu Cipcigan.

About this article

Publication history

Received 13 October 2017 Accepted 14 December 2017

Published 29 January 2018

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