Interfacial Structural Transition in Hydration Shells of a Polarizable Solute

Mohammadhasan Dinpajooh and Dmitry V. Matyushov
Phys. Rev. Lett. 114, 207801 – Published 22 May 2015
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Abstract

Electrostatics of polar solvation is typically described by harmonic free energy functionals. Polarizability contributes a negative polarization term that can make the harmonic free energy negative. The harmonic truncation fails in this regime. Simulations of polarizable ideal dipoles in water show that water’s susceptibility passes through a maximum in the range of polarizabilities zeroing the harmonic term out. The microscopic origin of the nonmonotonic behavior is an interfacial structural transition involving the density collapse of the first hydration layer and enhanced number of dangling OH bonds.

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  • Received 6 January 2015

DOI:https://doi.org/10.1103/PhysRevLett.114.207801

© 2015 American Physical Society

Authors & Affiliations

Mohammadhasan Dinpajooh and Dmitry V. Matyushov*

  • Department of Physics and Department of Chemistry and Biochemistry, Arizona State University, P.O. Box 871504, Tempe, Arizona 85287, USA

  • *dmitrym@asu.edu

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Issue

Vol. 114, Iss. 20 — 22 May 2015

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