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dc.contributor.authorSanvito, Stefanoen
dc.contributor.authorO'Regan, Daviden
dc.date.accessioned2020-01-28T15:57:12Z
dc.date.available2020-01-28T15:57:12Z
dc.date.issued2018en
dc.date.submitted2018en
dc.identifier.citationRoychoudhury, S. and O'Regan, D.D. and Sanvito, S., Wannier-function-based constrained DFT with nonorthogonality-correcting Pulay forces in application to the reorganization effects in graphene-adsorbed pentacene, Physical Review B, 97, 20, 2018, 085303-en
dc.identifier.otherYen
dc.identifier.urihttps://journals.aps.org/prb/abstract/10.1103/PhysRevB.97.205120
dc.identifier.urihttp://hdl.handle.net/2262/91405
dc.descriptionPUBLISHEDen
dc.descriptionAwarded the Karl Wilkinson Prize 2019.en
dc.description.abstractPulay terms arise in the Hellmann-Feynman forces in electronic-structure calculations when one employs a basis set made of localized orbitals that move with their host atoms. If the total energy of the system depends on a subspace population defined in terms of the localized orbitals across multiple atoms, then unconventional Pulay terms will emerge due to the variation of the orbital nonorthogonality with ionic translation. Here, we derive the required exact expressions for such terms, which cannot be eliminated by orbital orthonormalization. We have implemented these corrected ionic forces within the linear-scaling density functional theory (DFT) package onetep, and we have used constrained DFT to calculate the reorganization energy of a pentacene molecule adsorbed on a graphene flake. The calculations are performed by including ensemble DFT, corrections for periodic boundary conditions, and empirical Van der Waals interactions. For this system we find that tensorially invariant population analysis yields an adsorbate subspace population that is very close to integer-valued when based upon nonorthogonal Wannier functions, and also but less precisely so when using pseudoatomic functions. Thus, orbitals can provide a very effective population analysis for constrained DFT. Our calculations show that the reorganization energy of the adsorbed pentacene is typically lower than that of pentacene in the gas phase. We attribute this effect to steric hindrance.en
dc.format.extent085303en
dc.language.isoenen
dc.relation.ispartofseriesPhysical Review Ben
dc.relation.ispartofseries97en
dc.relation.ispartofseries20en
dc.rightsYen
dc.subjectWannier function methodsen
dc.subjectDensity functional theoryen
dc.subjectAtomic orbitalen
dc.subjectGrapheneen
dc.subjectOrganic semiconductorsen
dc.subjectPhotoemissionen
dc.titleWannier-function-based constrained DFT with nonorthogonality-correcting Pulay forces in application to the reorganization effects in graphene-adsorbed pentaceneen
dc.typeJournal Articleen
dc.type.supercollectionscholarly_publicationsen
dc.type.supercollectionrefereed_publicationsen
dc.identifier.peoplefinderurlhttp://people.tcd.ie/sanvitosen
dc.identifier.peoplefinderurlhttp://people.tcd.ie/oregand2en
dc.identifier.rssinternalid188797en
dc.identifier.doihttp://dx.doi.org/10.1103/PhysRevB.97.205120en
dc.rights.ecaccessrightsopenAccess
dc.identifier.orcid_id0000-0002-0291-715Xen


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