Microscopic formulation of nonlocal electrostatics in polar liquids embedding polarizable ions

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dc.contributor Aalto-yliopisto fi
dc.contributor Aalto University en
dc.contributor.author Buyukdagli, Sahin
dc.contributor.author Ala-Nissilä, Tapio
dc.date.accessioned 2015-04-27T09:00:39Z
dc.date.available 2015-04-27T09:00:39Z
dc.date.issued 2013
dc.identifier.citation Buyukdagli, Sahin & Ala-Nissilä, Tapio. 2013. Microscopic formulation of nonlocal electrostatics in polar liquids embedding polarizable ions. Physical Review E. Volume 87, Issue 6. P. 063201/1-14. ISSN 1539-3755 (printed). DOI: 10.1103/physreve.87.063201. en
dc.identifier.issn 1539-3755 (printed)
dc.identifier.uri https://aaltodoc.aalto.fi/handle/123456789/15768
dc.description.abstract Nonlocal electrostatic interactions associated with finite solvent size and ion polarizability are investigated within the mean-field linear response theory. To this end, we introduce a field-theoretic model of a polar liquid composed of linear multipole solvent molecules and embedding polarizable ions modeled as Drude oscillators. Unlike previous dipolar Poisson-Boltzmann formulations treating the solvent molecules as point dipoles, our model is able to qualitatively reproduce the non-local dielectric response behavior of polar liquids observed in molecular dynamics simulations and atomic force microscope experiments for water solvent at charged interfaces. The present theory explains the formation of the associated interfacial hydration layers in terms of a cooperative dipolar response mechanism driven by the reaction of the solvent molecules to their own polarization field. We also incorporate into the theory the relative multipole moments of water molecules obtained from quantum mechanical calculations and show that the multipolar contributions to the dielectric permittivity are largely dominated by the dipolar one. We find that this stems from the mutual cancellation of the first two interfacial hydration layers of opposite net charge for multipolar liquids. Within the same nonlocal dielectric response theory, we show that the induced ion polarizability reverses the interfacial ion density trends predicted by the Poisson-Boltzmann theory, resulting in a surface affinity of coions and exclusion of counterions. The results indicate that the consideration of the discrete charge composition of solvent molecules and ions is the key step towards a microscopic understanding of nonlocal electrostatic effects in polar solvents. en
dc.format.extent 063201/1-14
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher American Physical Society (APS) en
dc.relation.ispartofseries Physical Review E en
dc.relation.ispartofseries Volume 87, Issue 6
dc.rights © 2013 American Physical Society (APS). http://www.aps.org en
dc.subject.other Physics en
dc.title Microscopic formulation of nonlocal electrostatics in polar liquids embedding polarizable ions en
dc.type A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä fi
dc.description.version Peer reviewed en
dc.rights.holder American Physical Society (APS)
dc.contributor.school Perustieteiden korkeakoulu fi
dc.contributor.school School of Science en
dc.contributor.department Teknillisen fysiikan laitos fi
dc.contributor.department Department of Applied Physics en
dc.subject.keyword electrostatic interactions en
dc.subject.keyword ion polarizability en
dc.subject.keyword polar liquids en
dc.subject.keyword Drude oscillators en
dc.subject.keyword water molecules en
dc.identifier.urn URN:NBN:fi:aalto-201504272429
dc.type.dcmitype text en
dc.identifier.doi 10.1103/physreve.87.063201
dc.type.version Final published version en


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