Publication:
Systematic formulation of thermodynamic properties in the NpT ensemble

cris.virtual.departmentThermodynamik
cris.virtual.departmentThermodynamik
cris.virtual.department#PLACEHOLDER_PARENT_METADATA_VALUE#
cris.virtual.departmentbrowseThermodynamik
cris.virtual.departmentbrowseThermodynamik
cris.virtual.departmentbrowseThermodynamik
cris.virtual.departmentbrowseThermodynamik
cris.virtualsource.department96d8e6e1-6361-46c5-ae2c-a84605aadf12
cris.virtualsource.departmentf52145ee-13bc-4c6e-b5fd-d59dcd5c9ec1
cris.virtualsource.department#PLACEHOLDER_PARENT_METADATA_VALUE#
dc.contributor.authorStröker, Philipp
dc.contributor.authorHellmann, Robert
dc.contributor.authorMeier, Karsten
dc.date.issued2021-02
dc.description.abstractMolecular 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.
dc.description.versionNA
dc.identifier.doi10.1103/PhysRevE.103.023305
dc.identifier.issn2470-0053
dc.identifier.issn2470-0045
dc.identifier.pmid33736048
dc.identifier.scopus2-s2.0-85101264566
dc.identifier.urihttps://openhsu.ub.hsu-hh.de/handle/10.24405/14454
dc.language.isoen
dc.relation.journalPhysical review. E, Statistical, nonlinear, and soft matter physics
dc.relation.orgunitThermodynamik
dc.rights.accessRightsmetadata only access
dc.titleSystematic formulation of thermodynamic properties in the NpT ensemble
dc.typeResearch article
dspace.entity.typePublication
hsu.peerReviewed
hsu.uniBibliography
oaire.citation.endPage9
oaire.citation.issue2
oaire.citation.startPage1
oaire.citation.volume103
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