We present a combined density functional theory (DFT)/time-dependent density functional theory (TDDFT) study of the geometry, electronic structure, and absorption and emission properties of the tetranuclear "cubane" Cu(4)I(4)py(4) (py= pyridine) system. The geometry of the singlet ground state and of the two lowest triplet states of the title complex were optimized, followed by TDDFT excited-state calculations. This procedure allowed us to characterize the nature of the excited states involved in the absorption spectrum and those responsible for the dual emission bands observed for this complex. In agreement with earlier experimental proposals, we find that while in absorption the halide-to-pyridine charge-transfer excited state (XLCT*) has a lower energy than the cluster-centered excited state (CC*), a strong geometrical relaxation on the triplet cluster-centered state surface leads to a reverse order of the excited states in emission.

Electronic transitions involved in the absorption spectrum and dual luminescence of tetranuclear cubane [Cu4I4(pyridine)(4)] cluster : a density functional theory/time-dependent density functional theory investigation / F. De Angelis, S. Fantacci, A. Sgamellotti, E. Cariati, R. Ugo, P..C. Ford. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - 45:26(2006 Dec), pp. 10576-10584.

Electronic transitions involved in the absorption spectrum and dual luminescence of tetranuclear cubane [Cu4I4(pyridine)(4)] cluster : a density functional theory/time-dependent density functional theory investigation

E. Cariati;R. Ugo;
2006

Abstract

We present a combined density functional theory (DFT)/time-dependent density functional theory (TDDFT) study of the geometry, electronic structure, and absorption and emission properties of the tetranuclear "cubane" Cu(4)I(4)py(4) (py= pyridine) system. The geometry of the singlet ground state and of the two lowest triplet states of the title complex were optimized, followed by TDDFT excited-state calculations. This procedure allowed us to characterize the nature of the excited states involved in the absorption spectrum and those responsible for the dual emission bands observed for this complex. In agreement with earlier experimental proposals, we find that while in absorption the halide-to-pyridine charge-transfer excited state (XLCT*) has a lower energy than the cluster-centered excited state (CC*), a strong geometrical relaxation on the triplet cluster-centered state surface leads to a reverse order of the excited states in emission.
Settore CHIM/03 - Chimica Generale e Inorganica
dic-2006
Article (author)
File in questo prodotto:
Non ci sono file associati a questo prodotto.
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/30114
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 213
  • ???jsp.display-item.citation.isi??? 172
social impact