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

Journal Article · Wed Oct 28 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4934220· OSTI ID:22493172

Siepmann, J. Ilja ^[1]

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1. Department of Chemistry and Chemical Theory Center, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455 (United States)

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.

• OSTI ID: 22493172
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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