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: Contribución a una revistaArtículo

38 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 originalInglés
Número de artículo064117
PublicaciónJournal of Chemical Physics
Volumen129
N.º6
DOI
EstadoPublicada - 26 ago 2008

Áreas temáticas de ASJC Scopus

  • Física y astronomía (todo)
  • Química física y teórica

Huella Profundice en los temas de investigación de 'Dual descriptors within the framework of spin-polarized density functional theory'. En conjunto forman una huella única.

  • Citar esto