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dc.contributor.author
Scherlis Perel, Damian Ariel
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Cococcioni, Matteo
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Sit, Patrick
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Marzari, Nicola
dc.date.available
2020-04-28T22:35:45Z
dc.date.issued
2007-06-05
dc.identifier.citation
Scherlis Perel, Damian Ariel; Cococcioni, Matteo; Sit, Patrick; Marzari, Nicola; Simulation of heme using DFT + U: a step toward accurate spin-state energetics; American Chemical Society; Journal of Physical Chemistry B; 111; 25; 5-6-2007; 7384-7391
dc.identifier.issn
1520-6106
dc.identifier.uri
http://hdl.handle.net/11336/103858
dc.description.abstract
We investigate the DFT + U approach as a viable solution to describe the low-lying states of ligated and unligated iron heme complexes. Besides their central role in organometallic chemistry, these compounds represent a paradigmatic case where LDA, GGA, and common hybrid functionals fail to reproduce the experimental magnetic splittings. In particular, the imidazole pentacoordinated heme is incorrectly described as a triplet by all usual DFT flavors. In this study, we show that a U parameter close to 4 eV leads to spin transitions and molecular geometries in quantitative agreement with experiments and that DFT + U represents an appealing tool in the description of iron porphyrin complexes, at a much reduced cost compared to correlated quantum-chemistry methods. The possibility of obtaining the U parameter from first principles is explored through a self-consistent linear-response formulation. We find that this approach, which proved to be successful in other iron systems, produces in this case some overestimation with respect to the optimal values of U.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
SPIN STATES
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DFT+U
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IRON
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BIOINORGANIC CHEMISTRY
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PYRROLES
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PORPHYRINS
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LIGANDS
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Físico-Química, Ciencia de los Polímeros, Electroquímica
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.title
Simulation of heme using DFT + U: a step toward accurate spin-state energetics
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2020-04-22T15:40:28Z
dc.journal.volume
111
dc.journal.number
25
dc.journal.pagination
7384-7391
dc.journal.pais
Estados Unidos
dc.description.fil
Fil: Scherlis Perel, Damian Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
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Fil: Cococcioni, Matteo. University of Minnesota; Estados Unidos
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Fil: Sit, Patrick. Massachusetts Institute of Technology; Estados Unidos
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Fil: Marzari, Nicola. Massachusetts Institute of Technology; Estados Unidos
dc.journal.title
Journal of Physical Chemistry B
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/abs/10.1021/jp070549l?src=recsys
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/jp070549l
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