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Three-Dimensional Hard Dumbbell Solid Free Energy Calculation via the Fluctuating Cell Model

Published

Author(s)

S Kadlec, P D. Beale, James C. Rainwater

Abstract

Determination of the solid-liquid phase transition point of a molecular substance calculation of the free energy in both phases. Progress has been made on this problem by modeling molecules as fused hard spheres and adding attraction and electric multipole moments perturbatively. The solid free energy of hard heteronuclear dumbbells of bond length L*, used to model diatomic molecules, can in principle be calculated exactly via the Frenkel-Ladd method, but this is computationally expensive. Use of Lennard Jones-Devonshire fixed cells to calculate free energy is much simpler computationally but is an approximation. The fluctuating cell model is investigated as an alternate intermediate method which is still computationally simpler than Frenkel-Ladd. As was found earlier in two dimensions, for small L* the simple cell model is in better agreement with Frenkel-Ladd than the fluctuating cell model, but for larger L* the fluctuating cell model is in better agreement. The probability distributions of free volumes are also analyzed and show different functional behavior for near-zero bond length and appreciable bond length.
Citation
International Journal of Thermophysics
Volume
25
Issue
No. 5

Keywords

fluctuating cell model, free energy, hard dumbbell, simulation, solid

Citation

Kadlec, S. , Beale, P. and Rainwater, J. (2004), Three-Dimensional Hard Dumbbell Solid Free Energy Calculation via the Fluctuating Cell Model, International Journal of Thermophysics (Accessed June 22, 2024)

Issues

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Created September 1, 2004, Updated February 17, 2017