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Title: Bubble nucleation in simple and molecular liquids via the largest spherical cavity method

In this work, we propose a methodology to compute bubble nucleation free energy barriers using trajectories generated via molecular dynamics simulations. We follow the bubble nucleation process by means of a local order parameter, defined by the volume of the largest spherical cavity (LSC) formed in the nucleating trajectories. This order parameter simplifies considerably the monitoring of the nucleation events, as compared with the previous approaches which require ad hoc criteria to classify the atoms and molecules as liquid or vapor. The combination of the LSC and the mean first passage time technique can then be used to obtain the free energy curves. Upon computation of the cavity distribution function the nucleation rate and free-energy barrier can then be computed. We test our method against recent computations of bubble nucleation in simple liquids and water at negative pressures. We obtain free-energy barriers in good agreement with the previous works. The LSC method provides a versatile and computationally efficient route to estimate the volume of critical bubbles the nucleation rate and to compute bubble nucleation free-energies in both simple and molecular liquids.
Authors:
 [1] ;  [2] ; ;  [1] ;  [3] ;  [4]
  1. Departamento de Química Física, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid (Spain)
  2. (United Kingdom)
  3. Department of Chemistry, Imperial College London, London SW7 2AZ (United Kingdom)
  4. (Norway)
Publication Date:
OSTI Identifier:
22415689
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BUBBLES; COMPARATIVE EVALUATIONS; DIFFUSION BARRIERS; DISTRIBUTION FUNCTIONS; FREE ENERGY; LIQUIDS; MOLECULAR DYNAMICS METHOD; MOLECULES; NUCLEATION; ORDER PARAMETERS; SPHERICAL CONFIGURATION; VAPORS; WATER