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dc.contributor.author
Anderson, Lindsey N.
dc.contributor.author
Oviedo, María Belén
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dc.contributor.author
Wong, Bryan M.
dc.date.available
2018-10-04T13:10:03Z
dc.date.issued
2017-04-24
dc.identifier.citation
Anderson, Lindsey N.; Oviedo, María Belén; Wong, Bryan M.; Accurate Electron Affinities and Orbital Energies of Anions from a Nonempirically Tuned Range-Separated Density Functional Theory Approach; American Chemical Society; Journal of Chemical Theory and Computation; 13; 4; 24-4-2017; 1656-1666
dc.identifier.issn
1549-9618
dc.identifier.uri
http://hdl.handle.net/11336/61644
dc.description.abstract
The treatment of atomic anions with Kohn-Sham density functional theory (DFT) has long been controversial because the highest occupied molecular orbital (HOMO) energy, EHOMO, is often calculated to be positive with most approximate density functionals. We assess the accuracy of orbital energies and electron affinities for all three rows of elements in the periodic table (H-Ar) using a variety of theoretical approaches and customized basis sets. Among all of the theoretical methods studied here, we find that a nonempirically tuned range-separated approach (constructed to satisfy DFT-Koopmans' theorem for the anionic electron system) provides the best accuracy for a variety of basis sets, even for small basis sets where most functionals typically fail. Previous approaches to solve this conundrum of positive EHOMO values have utilized non-self-consistent methods; however, electronic properties, such as electronic couplings/gradients (which require a self-consistent potential and energy), become ill-defined with these approaches. In contrast, the nonempirically tuned range-separated procedure used here yields well-defined electronic couplings/gradients and correct EHOMO values because both the potential and resulting electronic energy are computed self-consistently. Orbital energies and electron affinities are further analyzed in the context of the electronic energy as a function of electronic number (including fractional numbers of electrons) to provide a stringent assessment of self-interaction errors for these complex anion systems.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
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dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Electron Affinity
dc.subject
Anions
dc.subject
Lc-Dft
dc.subject.classification
Otras Ciencias Químicas
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dc.subject.classification
Ciencias Químicas
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dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
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dc.title
Accurate Electron Affinities and Orbital Energies of Anions from a Nonempirically Tuned Range-Separated Density Functional Theory Approach
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2018-09-10T15:46:51Z
dc.identifier.eissn
1549-9626
dc.journal.volume
13
dc.journal.number
4
dc.journal.pagination
1656-1666
dc.journal.pais
Estados Unidos
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dc.journal.ciudad
Washington
dc.description.fil
Fil: Anderson, Lindsey N.. University of California; Estados Unidos
dc.description.fil
Fil: Oviedo, María Belén. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. University of California; Estados Unidos
dc.description.fil
Fil: Wong, Bryan M.. University of California; Estados Unidos
dc.journal.title
Journal of Chemical Theory and Computation
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dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.jctc.6b01249
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/acs.jctc.6b01249
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