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Title: Understanding the sensitivity of nucleation free energies: The role of supersaturation and temperature

Simulations are used to investigate the vapor-to-liquid nucleation of water for several different force fields at various sets of physical conditions. The nucleation free energy barrier is found to be extremely sensitive to the force field at the same absolute conditions. However, when the results are compared at the same supersaturation and reduced temperature or the same metastability parameter and reduced temperature, then the differences in the nucleation free energies of the different models are dramatically reduced. This finding suggests that comparisons of experimental data and computational predictions are most meaningful at the same relative conditions and emphasizes the importance of knowing the phase diagram of a given computational model, but such information is usually not available for models where the interaction energy is determined directly from electronic structure calculations.
Authors:
 [1] ;  [2] ;  [1] ;  [2]
  1. Department of Chemistry and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455 (United States)
  2. (United States)
Publication Date:
OSTI Identifier:
22493172
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 16; 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; COMPARATIVE EVALUATIONS; ELECTRONIC STRUCTURE; EXPERIMENTAL DATA; FREE ENERGY; INTERACTIONS; LIQUIDS; NUCLEATION; PHASE DIAGRAMS; SENSITIVITY; SIMULATION; SUPERSATURATION; VAPORS; WATER