title: Theory for an order-driven disruption of the liquid state in water.
abstract: Water is known to exhibit a number of peculiar physical properties because of the strong orientational dependence of the intermolecular hydrogen bonding interactions that dominate its liquid state. Recent full-atom simulations of water in a nanolayer between graphite plates submersed in an aqueous medium have raised the possibility of a new addition to this list of peculiarities: they show that application of a strong, uniform electric field normal to and between the plates can cause a pronounced decrease in particle density, rather than the increase expected from electrostriction theory for polarizable fluids [Vaitheeswaran et al., J. Phys. Chem. B 70, 6629 (2005)]. However, in seeming contradiction to this result, another study that simulated a range of similar systems has reported a less surprising electrostrictive increase in particle density upon application of the field [Bratko et al., J. Am. Chem. Soc. 129, 2504 (2007)]. In this work, we attempt to reconcile these conflicting simulation phenomena using a statistical mechanical lattice liquid model of water in an applied field. By solving the model using mean-field theory, we show that a field-induced transition to a markedly lower-density phase such as that observed in recent simulations is possible within a certain parameter regime, but that outside of this regime, the more conventional electrostrictive result should be obtained. Upon modifying the model to treat the case of bulk water under constant pressure in an applied field, we predict a density drop with rising field, and subsequently observe the predicted behavior in our own molecular dynamics simulations of liquid water. Our findings lead us to propose that the model considered here may be useful in a variety of contexts for describing the trade-off between orientational ordering of water molecules and their participation in the liquid phase.
authors.affiliation: Department of Physics, Stanford University, Stanford, California 94305, USA. jengland@stanford.edu
authors.forename: Jeremy L
authors.initials: JL
authors.lastname: England
authors.forename: Sanghyun
authors.initials: S
authors.lastname: Park
authors.forename: Vijay S
authors.initials: VS
authors.lastname: Pande
mesh_terms: D003198:Computer Simulation; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry; D057927:Hydrophobic and Hydrophilic Interactions; D008962:Models, Theoretical; D008968:Molecular Conformation; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D012997:Solvents; D014867:Water; D006859:Hydrogen