Bonding in tetrahedral Cu-4(mu(3)-X)(4)L-4 copper(I) clusters: A DFT investigation

Vega A.; Saillard, JY

Abstract

DFT calculations on Cu4(?3-X)4L 4 (X = H, CH3, CCH, F, Cl, Br, I; L = NH3, PH3) indicate that, regardless of its nature, X- acts essentially as a two-electron ?-type ligand and that the covalent part of the Cu?Cu bonding depends mainly upon the a1 component of the orbital interaction between the L4Cu44+ and X44- fragments. The first excited state corresponds to the occupation of a Cu?Cu bonding LUMO of a1 symmetry, which is of dominant Cu(4s/4p) character when X- is an electronegative ligand, such as a halide. Consequently, this excited state is computed to exhibit Cu?Cu distances shorter than those in the ground state, in agreement with the luminescence properties of this type of compound.

Más información

Título según WOS: Bonding in tetrahedral Cu-4(mu(3)-X)(4)L-4 copper(I) clusters: A DFT investigation
Título según SCOPUS: Bonding in tetrahedral Cu4(?3-X)4L 4 Copper(I) clusters: A DFT investigation
Título de la Revista: INORGANIC CHEMISTRY
Volumen: 43
Número: 13
Editorial: American Chemical Society
Fecha de publicación: 2004
Página de inicio: 4012
Página final: 4018
Idioma: English
URL: http://pubs.acs.org/doi/abs/10.1021/ic035262r
DOI:

10.1021/ic035262r

Notas: ISI, SCOPUS