Title: Systematic formulation of thermodynamic properties in the NpT ensemble
Authors: Ströker, Philipp
Hellmann, Robert 
Meier, Karsten 
Language: eng
Issue Date: Feb-2021
Document Type: Article
Journal / Series / Working Paper (HSU): Physical review. E, Statistical, nonlinear, and soft matter physics
Volume: 103
Issue: 2
Page Start: 1
Page End: 9
Abstract: 
Molecular expressions for thermodynamic properties and derivatives of the Gibbs energy up to third order in the isobaric-isothermal (NpT) ensemble are systematically derived using the methodology developed by Lustig for the microcanonical and canonical ensembles [J. Chem. Phys. 100, 3048 (1994)10.1063/1.466446; Mol. Phys. 110, 3041 (2012)10.1080/00268976.2012.695032]. They are expressed by phase-space functions, which represent derivatives of the Gibbs energy with respect to temperature and pressure. Additionally, expressions for the phase-space functions for temperature-dependent potentials are provided, which, for example, are required when quantum corrections, e.g., Feynman-Hibbs corrections, are applied in classical simulations. The derived expressions are validated by Monte Carlo simulations for the simple Lennard-Jones model fluid at three selected state points. A unique result is that the phase-space functions contain only ensemble averages of combinations of powers of enthalpy and volume. Thus, the calculation of thermodynamic properties in the NpT ensemble does not require volume derivatives of the potential energy. This is particularly advantageous in Monte Carlo simulations when the interactions between molecules are described by empirical force fields or very accurate ab initio pair and nonadditive three-body potentials.
Organization Units (connected with the publication): Thermodynamik 
ISSN: 24700045
Publisher DOI: 10.1103/PhysRevE.103.023305
Appears in Collections:3 - Reported Publications

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