Accurate schemes for calculation of thermodynamic properties of liquid mixtures from molecular dynamics simulations

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dc.contributorAalto-yliopistofi
dc.contributorAalto Universityen
dc.contributor.authorCaro, Miguel A.en_US
dc.contributor.authorLaurila, Tomien_US
dc.contributor.authorLopez-Acevedo, Olgaen_US
dc.contributor.departmentDepartment of Applied Physicsen
dc.contributor.departmentDepartment of Electrical Engineering and Automationen
dc.contributor.groupauthorComputational Electronic Structure Theoryen
dc.contributor.groupauthorComputational Soft and Molecular Matteren
dc.contributor.groupauthorMicrosystems Technologyen
dc.date.accessioned2018-08-01T12:43:05Z
dc.date.available2018-08-01T12:43:05Z
dc.date.issued2016-12-28en_US
dc.description.abstractWe explore different schemes for improved accuracy of entropy calculations in aqueous liquid mixtures from molecular dynamics (MD) simulations. We build upon the two-phase thermodynamic (2PT) model of Lin et al. [J. Chem. Phys. 119, 11792 (2003)] and explore new ways to obtain the partition between the gas-like and solid-like parts of the density of states, as well as the effect of the chosen ideal “combinatorial” entropy of mixing, both of which have a large impact on the results. We also propose a first-order correction to the issue of kinetic energy transfer between degrees of freedom (DoF). This problem arises when the effective temperatures of translational, rotational, and vibrational DoF are not equal, either due to poor equilibration or reduced system size/time sampling, which are typical problems for ab initio MD. The new scheme enables improved convergence of the results with respect to configurational sampling, by up to one order of magnitude, for short MD runs. To ensure a meaningful assessment, we perform MD simulations of liquid mixtures of water with several other molecules of varying sizes: methanol, acetonitrile, N, N-dimethylformamide, and n-butanol. Our analysis shows that results in excellent agreement with experiment can be obtained with little computational effort for some systems. However, the ability of the 2PT method to succeed in these calculations is strongly influenced by the choice of force field, the fluidicity (hard-sphere) formalism employed to obtain the solid/gas partition, and the assumed combinatorial entropy of mixing. We tested two popular force fields, GAFF and OPLS with SPC/E water. For the mixtures studied, the GAFF force field seems to perform as a slightly better “all-around” force field when compared to OPLS+SPC/E.en
dc.description.versionPeer revieweden
dc.format.mimetypeapplication/pdfen_US
dc.identifier.citationCaro, M A, Laurila, T & Lopez-Acevedo, O 2016, ' Accurate schemes for calculation of thermodynamic properties of liquid mixtures from molecular dynamics simulations ', Journal of Chemical Physics, vol. 145, no. 24, 244504 . https://doi.org/10.1063/1.4973001en
dc.identifier.doi10.1063/1.4973001en_US
dc.identifier.issn0021-9606
dc.identifier.issn1089-7690
dc.identifier.otherPURE UUID: 599ebf7f-bfed-436b-86a4-7ce10ef4ec07en_US
dc.identifier.otherPURE ITEMURL: https://research.aalto.fi/en/publications/599ebf7f-bfed-436b-86a4-7ce10ef4ec07en_US
dc.identifier.otherPURE LINK: http://www.scopus.com/inward/record.url?scp=85008686921&partnerID=8YFLogxKen_US
dc.identifier.otherPURE FILEURL: https://research.aalto.fi/files/26688584/1.4973001.pdfen_US
dc.identifier.urihttps://aaltodoc.aalto.fi/handle/123456789/32776
dc.identifier.urnURN:NBN:fi:aalto-201808014176
dc.language.isoenen
dc.relation.ispartofseriesJournal of Chemical Physicsen
dc.relation.ispartofseriesVolume 145, issue 24en
dc.rightsopenAccessen
dc.titleAccurate schemes for calculation of thermodynamic properties of liquid mixtures from molecular dynamics simulationsen
dc.typeA1 Alkuperäisartikkeli tieteellisessä aikakauslehdessäfi
dc.type.versionpublishedVersion
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