Path integral calculation of free energies: quantum effects on the melting temperature of neon.
The path integral formulation has been combined with several methods to determine free energies of quantum many-body systems, such as adiabatic switching and reversible scaling. These techniques are alternatives to the standard thermodynamic integration method. A quantum Einstein crystal is used as a model to demonstrate the accuracy and reliability of these free energy methods in quantum simulations. Our main interest focuses on the calculation of the melting temperature of Ne at ambient pressure, taking into account quantum effects in the atomic dynamics. The free energy of the solid was calculated by considering a quantum Einstein crystal as reference state, while for the liquid, the reference state was defined by the classical limit of the fluid. Our findings indicate that, while quantum effects in the melting temperature of this system are small, they still amount to about 6% of the melting temperature, and are therefore not negligible. The particle density as well as the melting enthalpy and entropy of the solid and liquid phases at coexistence is compared to results obtained in the classical limit and also to available experimental data.
Ramírez
R
R
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, Campus de Cantoblanco, 28049 Madrid, Spain. ramirez@icmm.csic.es
Herrero
C P
CP
Antonelli
A
A
Hernández
E R
ER