Solid-liquid critical behavior of water in nanopores

Kenji Mochizuki, Kenichiro Koga, Srikanth Sastry

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

Nanoconfined liquid water can transform into low-dimensional ices whose crystalline structures are dissimilar to any bulk ices and whose melting point may significantly rise with reducing the pore size, as revealed by computer simulation and confirmed by experiment. One of the intriguing, and as yet unresolved, questions concerns the observation that the liquid water may transform into a low-dimensional ice either via a first-order phase change or without any discontinuity in thermodynamic and dynamic properties, which suggests the existence of solid-liquid critical points in this class of nanoconfined systems. Here we explore the phase behavior of a model of water in carbon nanotubes in the temperature-pressure- diameter space by molecular dynamics simulation and provide unambiguous evidence to support solid-liquid critical phenomena of nanoconfined water. Solid-liquid first-order phase boundaries are determined by tracing spontaneous phase separation at various temperatures. All of the boundaries eventually cease to exist at the critical points and there appear loci of response function maxima, or the Widom lines, extending to the supercritical region. The finite-size scaling analysis of the density distribution supports the presence of both first-order and continuous phase changes between solid and liquid. At around the Widom line, there are microscopic domains of two phases, and continuous solid-liquid phase changes occur in such a way that the domains of one phase grow and those of the other evanesce as the thermodynamic state departs from the Widom line.

Original languageEnglish
Pages (from-to)8221-8226
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume112
Issue number27
DOIs
Publication statusPublished - Jul 7 2015

Keywords

  • Carbon nanotube
  • Ice
  • Solid-liquid critical point
  • Water
  • Widom line

ASJC Scopus subject areas

  • General

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