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dc.contributor.authorShi, Benjamin
dc.contributor.authorKapil, Venkat
dc.contributor.authorZen, Andrea
dc.contributor.authorChen, Ji
dc.contributor.authorAlavi, Ali
dc.contributor.authorMichaelides, Angelos
dc.date.accessioned2022-04-07T23:30:10Z
dc.date.available2022-04-07T23:30:10Z
dc.date.issued2022-03-28
dc.identifier.issn0021-9606
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/335892
dc.description.abstractThe O vacancy (Ov) formation energy, EOv, is an important property of a metal-oxide, governing its performance in applications such as fuel cells or heterogeneous catalysis. These defects are routinely studied with density functional theory (DFT). However, it is well-recognized that standard DFT formulations (e.g., the generalized gradient approximation) are insufficient for modeling the Ov, requiring higher levels of theory. The embedded cluster method offers a promising approach to compute EOv accurately, giving access to all electronic structure methods. Central to this approach is the construction of quantum(-mechanically treated) clusters placed within suitable embedding environments. Unfortunately, current approaches to constructing the quantum clusters either require large system sizes, preventing application of high-level methods, or require significant manual input, preventing investigations of multiple systems simultaneously. In this work, we present a systematic and general quantum cluster design protocol that can determine small converged quantum clusters for studying the Ov in metal-oxides with accurate methods, such as local coupled cluster with single, double, and perturbative triple excitations. We apply this protocol to study the Ov in the bulk and surface planes of rutile TiO2 and rock salt MgO, producing the first accurate and well-converged determinations of EOv with this method. These reference values are used to benchmark exchange-correlation functionals in DFT, and we find that all the studied functionals underestimate EOv, with the average error decreasing along the rungs of Jacob's ladder. This protocol is automatable for high-throughput calculations and can be generalized to study other point defects or adsorbates.
dc.publisherAIP Publishing
dc.rightsAll Rights Reserved
dc.rights.urihttp://www.rioxx.net/licenses/all-rights-reserved
dc.subjectcond-mat.mtrl-sci
dc.subjectcond-mat.mtrl-sci
dc.subjectphysics.chem-ph
dc.titleGeneral embedded cluster protocol for accurate modeling of oxygen vacancies in metal-oxides.
dc.typeArticle
dc.publisher.departmentDepartment of Chemistry Student
dc.publisher.departmentDepartment of Chemistry
dc.date.updated2022-04-06T16:25:23Z
prism.endingPage124704
prism.issueIdentifier12
prism.publicationDate2022
prism.publicationNameJ Chem Phys
prism.startingPage124704
prism.volume156
dc.identifier.doi10.17863/CAM.83326
dcterms.dateAccepted2022-03-10
rioxxterms.versionofrecord10.1063/5.0087031
rioxxterms.versionAM
dc.contributor.orcidShi, Benjamin [0000-0003-3272-0996]
dc.contributor.orcidAlavi, Ali [0000-0002-0654-9489]
dc.contributor.orcidMichaelides, Angelos [0000-0002-9169-169X]
dc.identifier.eissn1089-7690
dc.publisher.urlhttp://dx.doi.org/10.1063/5.0087031
rioxxterms.typeJournal Article/Review
pubs.funder-project-idEPSRC (EP/T022159/1)
datacite.issupplementedby.urlhttps://doi.org/10.17863/CAM.83268
cam.orpheus.success2022-04-07 - Embargo set during processing via Fast-track
cam.depositDate2022-04-06
pubs.licence-identifierapollo-deposit-licence-2-1
pubs.licence-display-nameApollo Repository Deposit Licence Agreement
rioxxterms.freetoread.startdate2022-03-28


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