On the computation of electrical conductivities of aqueous electrolyte solutions: Two surfaces one property

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dc.contributor.authorBlázquez Fernández, Samuel
dc.contributor.authorFernández Abascal, José Luis
dc.contributor.authorLagerweij, Jelle
dc.contributor.authorHabibi, Parsa
dc.contributor.authorDey, Poloumy
dc.contributor.authorVlugt, Thijs
dc.contributor.authorMoultos, Othonas
dc.contributor.authorVega De Las Heras, Carlos
dc.date.accessioned2023-11-22T14:47:30Z
dc.date.available2023-11-22T14:47:30Z
dc.date.issued2023
dc.description.abstractIn this work, we have computed electrical conductivities at ambient conditions of aqueous NaCl and KCl solutions by using the Einstein-Helfand equation. Common force fields (charge q =±1 e) do not reproduce the experimental values of electrical conductivities, viscosities and diffusion coefficients. Recently, we proposed the idea of using different charges to describe the Potential Energy Surface (PES) and the Dipole Moment Surface (DMS). In this work, we implement this concept. The equilibrium trajectories required to evaluate electrical conductivities (within linear response theory) were obtained by using scaled charges (with the value q =±0.75 e) to describe the PES. The potential parameters were those of the Madrid-Transport force field, which describe accurately viscosities and diffusion coefficients of these ionic solutions. However, integer charges were used to compute the conductivities (thus describing the DMS). The basic idea is that although the scaled charge describes the ion-water interaction better, the integer charge reflects the value of the charge that is transported due to the electric field. The agreement obtained with experiments is excellent, as for the first time electrical conductivities (and the other transport properties) of NaCl and KCl electrolyte solutions are described with high accuracy for the whole concentration range up to their solubility limit. Finally, we propose an easy way to obtain a rough estimate of the actual electrical conductivity of the potential model under consideration using the approximate Nernst-Einstein equation, which neglects correlations between different ions.
dc.description.departmentDepto. de Química Física
dc.description.facultyFac. de Ciencias Químicas
dc.description.refereedTRUE
dc.description.statussubmitted
dc.identifier.citationSamuel Blazquez, Jose L. F. Abascal, Jelle Lagerweij, Parsa Habibi, Poulumi Dey, Thijs J. H. Vlugt, Othonas A. Moultos, and Carlos Vega Journal of Chemical Theory and Computation 2023 19 (16), 5380-5393 DOI: 10.1021/acs.jctc.3c00562
dc.identifier.doi10.1021/acs.jctc.3c00562
dc.identifier.issn1549-9618
dc.identifier.officialurlhttps://doi.org/10.1021/acs.jctc.3c00562
dc.identifier.urihttps://hdl.handle.net/20.500.14352/88914
dc.issue.number16
dc.journal.titleJournal of Chemical Theory and Computation
dc.language.isoeng
dc.page.final5393
dc.page.initial5380
dc.publisherAmerican Chemical Society
dc.relation.projectIDPID2019- 105898GB-C21
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internationalen
dc.rights.accessRightsopen access
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.cdu544
dc.subject.keywordElectrical conductivity
dc.subject.keywordIons
dc.subject.keywordMolecular mechanics
dc.subject.keywordTransport properties
dc.subject.keywordViscosity
dc.subject.ucmQuímica física (Química)
dc.subject.unesco2307 Química Física
dc.titleOn the computation of electrical conductivities of aqueous electrolyte solutions: Two surfaces one property
dc.typejournal article
dc.type.hasVersionAO
dc.volume.number19
dspace.entity.typePublication
relation.isAuthorOfPublication5e615c55-6488-4b22-b305-54e3b2eddc0a
relation.isAuthorOfPublication01d892ab-5d1d-4598-b1a6-3d25d4838908
relation.isAuthorOfPublicationafc0dec4-60b1-45f4-b844-1486ea139189
relation.isAuthorOfPublication.latestForDiscoveryafc0dec4-60b1-45f4-b844-1486ea139189
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