Collect. Czech. Chem. Commun. 2003, 68, 627-643

Calculation of Thermodynamical, Transport and Structural Properties of Neon in Liquid and Supercritical Phases by Molecular Dynamics Simulations Using an Accurate ab initio Pair Potential

Muthusamy Venkatraja, Markus G. Müllera, Hanspeter Hubera,* and Robert J. Gdanitzb

a Departement Chemie, Universität Basel, Klingelbergstrasse 80, CH-4056, Basel, Switzerland
b Department of Chemistry, University of Utah, 315 S. 1400 E, Rm 2020, Salt Lake City, UT 84112, U.S.A.


An analytical potential energy curve (NE3) is constructed from points obtained by accurate ab initio calculations. The quality of the pair potential is established by a comparison of calculated and experimental second virial coefficients as a function of temperature. Molecular dynamics equilibrium simulations are performed with the NE3 potential for pressures between 20 and 1000 MPa and temperatures between 100 and 600 K in the supercritical phase and for one point in the liquid phase of neon. The properties are compared with those obtained from experiment. It is found that the accurate pair potential has a large effect on pressure, energies and enthalpies and a significant influence on other thermodynamic properties but little influence on transport and structural properties. In the supercritical phase the deviation between the calculated quantum-corrected and experimental pressure values is always less than 2%.

Keywords: Molecular dynamics simulations; Neon; Thermodynamics; Ab initio pair potential; Computational chemistry.

References: 41 live references.