Free energy barriers to evaporation of water in hydrophobic confinement

Sumit Sharma, Pablo G. Debenedetti

Research output: Contribution to journalArticle

41 Scopus citations

Abstract

We use umbrella sampling Monte Carlo and forward and reverse forward flux sampling (FFS) simulation techniques to compute the free energy barriers to evaporation of water confined between two hydrophobic surfaces separated by nanoscopic gaps, as a function of the gap width, at 1 bar and 298 K. The evaporation mechanism for small (1 × 1 nm2) surfaces is found to be fundamentally different from that for large (3 × 3 nm2) surfaces. In the latter case, the evaporation proceeds via the formation of a gap-spanning tubular cavity. The 1 × 1 nm2 surfaces, in contrast, are too small to accommodate a stable vapor cavity. Accordingly, the associated free energy barriers correspond to the formation of a critical-sized cavity for sufficiently large confining surfaces, and to complete emptying of the gap region for small confining surfaces. The free energy barriers to evaporation were found to be of O(20kT) for 14 Å gaps, and to increase by approximately ∼5kT with every 1 Å increase in the gap width. The entropy contribution to the free energy of evaporation was found to be independent of the gap width.

Original languageEnglish (US)
Pages (from-to)13282-13289
Number of pages8
JournalJournal of Physical Chemistry B
Volume116
Issue number44
DOIs
StatePublished - Nov 8 2012

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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