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...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-04, Vol.142 (15), p.154903-154903
Main Authors: Gonzalez, Miguel A, Abascal, José L F, Valeriani, Chantal, Bresme, Fernando
Format: Article
Language:English
Subjects:
Barriers
BUBBLES
COMPARATIVE EVALUATIONS
Computer simulation
DIFFUSION BARRIERS
DISTRIBUTION FUNCTIONS
FREE ENERGY
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
LIQUIDS
Molecular dynamics
MOLECULAR DYNAMICS METHOD
MOLECULES
NUCLEATION
ORDER PARAMETERS
Physics
SPHERICAL CONFIGURATION
Test procedures
Trajectories
VAPORS
WATER
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Summary: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.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4916919