Alternative first-principles calculation of entropy for liquids

Edmund R. Meyer, Christopher Ticknor, Joel D. Kress, and Lee A. Collins
Phys. Rev. E 93, 042119 – Published 15 April 2016

Abstract

We present an alternative method for interpreting the velocity autocorrelation function (VACF) of a fluid with application to extracting the entropy in a manner similar to the methods developed by Lin et al. [J. Chem. Phys. 119, 11792 (2003)] and improved upon by Desjarlais [Phys. Rev. E 88, 062145 (2013)]. The liquid VACF is decomposed into two components, one gas and one solid, and each contribution's entropic portion is calculated. However, we fit both the gas and solid portions of the VACF in the time domain. This approach is applied to a single-component liquid (a two-phase model of liquid Al at the melt line) and two different two-component systems: a superionic-to-superionic (bcc to fcc) phase transition in H2O at high temperatures and pressures and a metastable liquid state of MgO. For all three examples, comparisons to existing results in the literature demonstrate the validity of our alternative.

  • Figure
  • Figure
  • Received 3 December 2015
  • Revised 24 March 2016

DOI:https://doi.org/10.1103/PhysRevE.93.042119

©2016 American Physical Society

Physics Subject Headings (PhySH)

  1. Physical Systems
Statistical Physics & Thermodynamics

Authors & Affiliations

Edmund R. Meyer*, Christopher Ticknor, Joel D. Kress, and Lee A. Collins

  • Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA

  • *meyere@lanl.gov

Article Text (Subscription Required)

Click to Expand

References (Subscription Required)

Click to Expand
Issue

Vol. 93, Iss. 4 — April 2016

Reuse & Permissions
Access Options
CHORUS

Article Available via CHORUS

Download Accepted Manuscript
Author publication services for translation and copyediting assistance advertisement

Authorization Required


×
×

Images

×

Sign up to receive regular email alerts from Physical Review E

Log In

Cancel
×

Search


Article Lookup

Paste a citation or DOI

Enter a citation
×