Density of states partitioning method for calculating the free energy of solids

Hainam Do, Richard J. Wheatley

Research output: Journal PublicationArticlepeer-review

15 Citations (Scopus)

Abstract

We propose a new simulation method, which combines a cage model and a density of states partitioning technique, to compute the free energy of an arbitrary solid. The excess free energy is separated into two contributions, noninteracting and interacting. The excess free energy of the noninteracting solid is computed by partitioning its geometrical configuration space with respect to the ideal gas. This quantity depends on the lattice type and the number of molecules. The excess free energy of the interacting solid, with respect to the noninteracting solid, is calculated using density of states partitioning and a cage model. The cage model is better than the cell model in that it has a smaller configuration space and better represents the equilibrium distribution of solid configurations. Since the partition function (and hence free energy) is obtained from the density of states, which is independent of the temperature, equilibrium thermodynamic properties at any condition can be obtained by varying the density. We illustrate our method in the context of the free energy of dry ice.

Original languageEnglish
Pages (from-to)165-171
Number of pages7
JournalJournal of Chemical Theory and Computation
Volume9
Issue number1
DOIs
Publication statusPublished - 8 Jan 2013
Externally publishedYes

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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