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A theory for the stabilization of polar crystal surfaces by a liquid environment.

cam.depositDate2022-09-01
cam.issuedOnline2022-09-01
datacite.issupplementedby.doi10.17863/CAM.83994
dc.contributor.authorCox, Stephen J
dc.contributor.orcidCox, Stephen J [0000-0003-2708-8711]
dc.date.accessioned2022-09-12T23:30:13Z
dc.date.available2022-09-12T23:30:13Z
dc.date.issued2022-09-07
dc.date.updated2022-09-01T14:48:16Z
dc.description.abstractPolar crystal surfaces play an important role in the functionality of many materials and have been studied extensively over many decades. In this article, a theoretical framework is presented that extends existing theories by placing the surrounding solution environment on an equal footing with the crystal itself; this is advantageous, e.g., when considering processes such as crystal growth from solution. By considering the polar crystal as a stack of parallel plate capacitors immersed in a solution environment, the equilibrium adsorbed surface charge density is derived by minimizing the free energy of the system. In analogy to the well-known diverging surface energy of a polar crystal surface at zero temperature, for a crystal in solution it is shown that the "polar catastrophe" manifests as a diverging free energy cost to perturb the system from equilibrium. Going further than existing theories, the present formulation predicts that fluctuations in the adsorbed surface charge density become increasingly suppressed with increasing crystal thickness. We also show how, in the slab geometry often employed in both theoretical and computational studies of interfaces, an electric displacement field emerges as an electrostatic boundary condition, the origins of which are rooted in the slab geometry itself, rather than the use of periodic boundary conditions. This aspect of the work provides a firmer theoretical basis for the recent observation that standard "slab corrections" fail to correctly describe, even qualitatively, polar crystal surfaces in solution.
dc.description.sponsorshipRoyal Society
dc.identifier.doi10.17863/CAM.88400
dc.identifier.eissn1089-7690
dc.identifier.issn0021-9606
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/340963
dc.language.isoeng
dc.publisherAIP Publishing
dc.publisher.departmentDepartment of Chemistry
dc.publisher.urlhttp://dx.doi.org/10.1063/5.0097531
dc.rightsAttribution 4.0 International
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/
dc.subjectcond-mat.stat-mech
dc.subjectcond-mat.stat-mech
dc.titleA theory for the stabilization of polar crystal surfaces by a liquid environment.
dc.typeArticle
dcterms.dateAccepted2022-08-01
prism.publicationDate2022
prism.publicationNameJ Chem Phys
pubs.licence-display-nameApollo Repository Deposit Licence Agreement
pubs.licence-identifierapollo-deposit-licence-2-1
rioxxterms.typeJournal Article/Review
rioxxterms.versionVoR
rioxxterms.versionofrecord10.1063/5.0097531

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