Dual descriptors within the framework of spin-polarized density functional theory

E. Chamorro, P. Pérez, M. Duque, F. De Proft, P. Geerlings

Resultado de la investigación: Article

37 Citas (Scopus)

Resumen

Spin-polarized density functional theory (SP-DFT) allows both the analysis of charge-transfer (e.g., electrophilic and nucleophilic reactivity) and of spin-polarization processes (e.g., photophysical changes arising from electron transitions). In analogy with the dual descriptor introduced by Morell [J. Phys. Chem. A 109, 205 (2005)], we introduce new dual descriptors intended to simultaneously give information of the molecular regions where the spin-polarization process linking states of different multiplicity will drive electron density and spin density changes. The electronic charge and spin rearrangement in the spin forbidden radiative transitions S0 →T (n, π*) and S0 →T (π, π*) in formaldehyde and ethylene, respectively, have been used as benchmark examples illustrating the usefulness of the new spin-polarization dual descriptors. These quantities indicate those regions where spin-orbit coupling effects are at work in such processes. Additionally, the qualitative relationship between the topology of the spin-polarization dual descriptors and the vertical singlet triplet energy gap in simple substituted carbene series has been also discussed. It is shown that the electron density and spin density rearrangements arise in agreement with spectroscopic experimental evidence and other theoretical results on the selected target systems.

Idioma originalEnglish
Número de artículo064117
PublicaciónJournal of Chemical Physics
Volumen129
N.º6
DOI
EstadoPublished - 26 ago 2008

Huella dactilar

Spin polarization
Density functional theory
density functional theory
Carrier concentration
polarization
Electron transitions
electron spin
Formaldehyde
Charge transfer
Orbits
Energy gap
Topology
electron transitions
carbenes
formaldehyde
ethylene
topology
reactivity
charge transfer
orbits

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Citar esto

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abstract = "Spin-polarized density functional theory (SP-DFT) allows both the analysis of charge-transfer (e.g., electrophilic and nucleophilic reactivity) and of spin-polarization processes (e.g., photophysical changes arising from electron transitions). In analogy with the dual descriptor introduced by Morell [J. Phys. Chem. A 109, 205 (2005)], we introduce new dual descriptors intended to simultaneously give information of the molecular regions where the spin-polarization process linking states of different multiplicity will drive electron density and spin density changes. The electronic charge and spin rearrangement in the spin forbidden radiative transitions S0 →T (n, π*) and S0 →T (π, π*) in formaldehyde and ethylene, respectively, have been used as benchmark examples illustrating the usefulness of the new spin-polarization dual descriptors. These quantities indicate those regions where spin-orbit coupling effects are at work in such processes. Additionally, the qualitative relationship between the topology of the spin-polarization dual descriptors and the vertical singlet triplet energy gap in simple substituted carbene series has been also discussed. It is shown that the electron density and spin density rearrangements arise in agreement with spectroscopic experimental evidence and other theoretical results on the selected target systems.",
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Dual descriptors within the framework of spin-polarized density functional theory. / Chamorro, E.; Pérez, P.; Duque, M.; De Proft, F.; Geerlings, P.

En: Journal of Chemical Physics, Vol. 129, N.º 6, 064117, 26.08.2008.

Resultado de la investigación: Article

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T1 - Dual descriptors within the framework of spin-polarized density functional theory

AU - Chamorro, E.

AU - Pérez, P.

AU - Duque, M.

AU - De Proft, F.

AU - Geerlings, P.

PY - 2008/8/26

Y1 - 2008/8/26

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