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This content will become publicly available on March 22, 2017

Title: Determination of anharmonic free energy contributions: Low temperature phases of the Lennard-Jones system

We investigate a general method to calculate the free energy of crystalline solids by considering the harmonic approximation and quasistatically switching the anharmonic contribution. The advantage of this method is that the harmonic approximation provides an already very accurate estimate of the free energy, and therefore the anharmonic term is numerically very small and can be determined to high accuracy. We further show that the anharmonic contribution to the free energy satisfies a number of exact inequalities that place constraints on its magnitude and allows approximate but fast and accurate estimates. The method is implemented into a readily available general software by combining the code HOODLT (Highly Optimized Object Oriented Dynamic Lattice Theory) for the harmonic part and the molecular dynamics (MD) simulation package HOOMD-blue for the anharmonic part. We use the method to calculate the low temperature phase diagram for Lennard-Jones particles. We demonstrate that hcp is the equilibrium phase at low temperature and pressure and obtain the coexistence curve with the fcc phase, which exhibits reentrant behavior. Furthermore, several implications of the method are discussed.
 [1] ;  [2] ;  [2]
  1. Boston Univ., Boston, MA (United States); Univ. de Barcelona, Barcelona (Spain)
  2. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
OSTI Identifier:
Report Number(s):
Journal ID: ISSN 0021-9606; JCPSA6
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 12; Journal ID: ISSN 0021-9606
American Institute of Physics (AIP)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
Country of Publication:
United States
36 MATERIALS SCIENCE free energy; phase coexistence; Lennard-Jones potential; inequalities; phase diagram; lattice theory; computer software