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Thermodynamic properties and homogeneous nucleation rates for surface-melted physical clusters

McClurg, Richard B. and Flagan, Richard C. and Goddard, Willam A., III (1996) Thermodynamic properties and homogeneous nucleation rates for surface-melted physical clusters. Journal of Chemical Physics, 105 (17). pp. 7648-7663. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:MCCjcp96

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Abstract

We predict the free energy of van der Waals clusters (Fn) in the surface-melted temperature regime. These free energies are used to predict the bulk chemical potential, surface tension, Tolman length, and vapor pressure of noble gas crystals. Together, these estimates allow us to make definitive tests of the capillarity approximation in classical homogeneous nucleation theory. We find that the capillarity approximation underestimates the nucleation rate by thirty orders of magnitude for argon. The best available experiments are consistent with our calculation of nucleation rate as a function of temperature and pressure. We suggest experimental conditions appropriate for determining quantitative nucleation rates which would be invaluable in guiding further development of the theory. To make the predictions of Fn, we develop the Shellwise Lattice Search (SLS) algorithm to identify isomer fragments and the Linear Group Contribution (LGC) method to estimate the energy of isomers composed of those fragments. Together, SLS/LGC approximates the distribution of isomers which contribute to the configurational partition function (for up to 147-atom clusters). Estimates of the remaining free energy contributions come from a previous paper in this series.


Item Type:Article
Additional Information:©1996 American Institute of Physics. (Received 12 September 1995; accepted 19 July 1996) We thank Jon Doye and Professor D. J. Wales for providing the data from their prior work (Ref. 38) which we have included in Figure 5. RBM acknowledges a National Science Foundation Graduate Research Fellowship. Partial support of the work was provided by grants from the NSF (CHE 94-13930, CTS 91-13191, and ASC 92-17368) and from the International Fine Particle Research Institute. Portions of this research were performed using the Intel Delta System operated by Caltech on behalf of the Concurrent Supercomputing Consortium. We thank Donald Dabdub for his expertise in preparing our code for the Delta System and for handling the scheduling of the runs. The facilities of the MSC are also supported by grants from DOE-BCTR, Allied-Signal Corp., Asahi Chemical, Asahi Glass, Chevron Petroleum Technology Co., Chevron Research Technology Co., Hughes Research Laboratories, and Beckman Institute. Erratum: "Thermodynamic properties and homogeneous nucleation rates for surface-melted physical clusters" [J. Chem. Phys. 105, 7648 (1996)] Richard B. McClurg et al. J. Chem. Phys. 107, 7001 (1997)
Subject Keywords:MOLECULAR CLUSTERS; VAN DER WAALS BINDING; THERMODYNAMICS; FREE ENERGY; NUCLEATION; MELTING; CHEMICAL POTENTIAL; SURFACE TENSION; COMPUTERIZED SIMULATION
Record Number:CaltechAUTHORS:MCCjcp96
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:MCCjcp96
Alternative URL:http://dx.doi.org/10.1063/1.473002
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:1155
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:24 Dec 2005
Last Modified:26 Dec 2012 08:43

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