Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces

Handle URI:
http://hdl.handle.net/10754/552845
Title:
Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces
Authors:
Souza, A. M.; Rungger, I.; Pemmaraju, C. D.; Schwingenschlögl, Udo ( 0000-0003-4179-7231 ) ; Sanvito, S.
Abstract:
We present a computational scheme for extracting the energy-level alignment of a metal/molecule interface, based on constrained density functional theory and local exchange and correlation functionals. The method, applied here to benzene on Li(100), allows us to evaluate charge-transfer energies, as well as the spatial distribution of the image charge induced on the metal surface. We systematically study the energies for charge transfer from the molecule to the substrate as function of the molecule-substrate distance, and investigate the effects arising from image-charge confinement and local charge neutrality violation. For benzene on Li(100) we find that the image-charge plane is located at about 1.8 Å above the Li surface, and that our calculated charge-transfer energies compare perfectly with those obtained with a classical electrostatic model having the image plane located at the same position. The methodology outlined here can be applied to study any metal/organic interface in the weak coupling limit at the computational cost of a total energy calculation. Most importantly, as the scheme is based on total energies and not on correcting the Kohn-Sham quasiparticle spectrum, accurate results can be obtained with local/semilocal exchange and correlation functionals. This enables a systematic approach to convergence.
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Citation:
Constrained-DFT method for accurate energy-level alignment of metal/molecule interfaces 2013, 88 (16) Physical Review B
Journal:
Physical Review B
Issue Date:
7-Oct-2013
DOI:
10.1103/PhysRevB.88.165112
Type:
Article
ISSN:
1098-0121; 1550-235X
Additional Links:
http://link.aps.org/doi/10.1103/PhysRevB.88.165112; http://arxiv.org/abs/1309.6981
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorSouza, A. M.en
dc.contributor.authorRungger, I.en
dc.contributor.authorPemmaraju, C. D.en
dc.contributor.authorSchwingenschlögl, Udoen
dc.contributor.authorSanvito, S.en
dc.date.accessioned2015-05-14T12:08:45Zen
dc.date.available2015-05-14T12:08:45Zen
dc.date.issued2013-10-07en
dc.identifier.citationConstrained-DFT method for accurate energy-level alignment of metal/molecule interfaces 2013, 88 (16) Physical Review Ben
dc.identifier.issn1098-0121en
dc.identifier.issn1550-235Xen
dc.identifier.doi10.1103/PhysRevB.88.165112en
dc.identifier.urihttp://hdl.handle.net/10754/552845en
dc.description.abstractWe present a computational scheme for extracting the energy-level alignment of a metal/molecule interface, based on constrained density functional theory and local exchange and correlation functionals. The method, applied here to benzene on Li(100), allows us to evaluate charge-transfer energies, as well as the spatial distribution of the image charge induced on the metal surface. We systematically study the energies for charge transfer from the molecule to the substrate as function of the molecule-substrate distance, and investigate the effects arising from image-charge confinement and local charge neutrality violation. For benzene on Li(100) we find that the image-charge plane is located at about 1.8 Å above the Li surface, and that our calculated charge-transfer energies compare perfectly with those obtained with a classical electrostatic model having the image plane located at the same position. The methodology outlined here can be applied to study any metal/organic interface in the weak coupling limit at the computational cost of a total energy calculation. Most importantly, as the scheme is based on total energies and not on correcting the Kohn-Sham quasiparticle spectrum, accurate results can be obtained with local/semilocal exchange and correlation functionals. This enables a systematic approach to convergence.en
dc.relation.urlhttp://link.aps.org/doi/10.1103/PhysRevB.88.165112en
dc.relation.urlhttp://arxiv.org/abs/1309.6981en
dc.rightsArchived with thanks to Physical Review Ben
dc.titleConstrained-DFT method for accurate energy-level alignment of metal/molecule interfacesen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalPhysical Review Ben
dc.eprint.versionPublisher's Version/PDFen
dc.contributor.institutionSchool of Physics and CRANN, Trinity College, Dublin 2, Irelanden
dc.identifier.arxividarXiv:1309.6981en
kaust.authorSchwingenschlögl, Udoen
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