Signature properties of water: Their molecular electronic origins.
Water challenges our fundamental understanding of emergent materials properties from a molecular perspective. It exhibits a uniquely rich phenomenology including dramatic variations in behavior over the wide temperature range of the liquid into water's crystalline phases and amorphous states. We show that many-body responses arising from water's electronic structure are essential mechanisms harnessed by the molecule to encode for the distinguishing features of its condensed states. We treat the complete set of these many-body responses nonperturbatively within a coarse-grained electronic structure derived exclusively from single-molecule properties. Such a "strong coupling" approach generates interaction terms of all symmetries to all orders, thereby enabling unique transferability to diverse local environments such as those encountered along the coexistence curve. The symmetries of local motifs that can potentially emerge are not known a priori. Consequently, electronic responses unfiltered by artificial truncation are then required to embody the terms that tip the balance to the correct set of structures. Therefore, our fully responsive molecular model produces, a simple, accurate, and intuitive picture of water's complexity and its molecular origin, predicting water's signature physical properties from ice, through liquid-vapor coexistence, to the critical point.
National Physical Laboratory, Teddington, Middlesex TW11 0LW, United Kingdom; vlad.sokhan@npl.co.uk.
Vlad P
http://orcid.org/0000-0002-0753-9741
VP
Sokhan
School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3JZ, United Kingdom; and.
Andrew P
AP
Jones
School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3JZ, United Kingdom; and.
Flaviu S
FS
Cipcigan
National Physical Laboratory, Teddington, Middlesex TW11 0LW, United Kingdom; School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3JZ, United Kingdom; and.
Jason
J
Crain
School of Physics and Astronomy, The University of Edinburgh, Edinburgh EH9 3JZ, United Kingdom; and IBM Thomas J. Watson Research Center, Yorktown Heights, NY 10598.
Glenn J
GJ
Martyna
coarse-grained model; electronic responses; intermolecular interactions; many-body dispersion; subcritical water