Ab initio CASSCF/CASPT2 calculations have been carried out on the V2N2H6 complex, as a model of a series of (cyclobutane)diazadivanadium complexes, in order to study the electronic structure and bonding in these complexes. Analogous calculations were performed also on the cationic and anionic species in order to study the behavior of the complexes toward oxidation and reduction. Geometry optimizations have been performed on the lowest singlet and triplet states and on the ground states of the ions, using wave functions of the restricted active space (RAS) SCF type. Dynamic correlation effects are included by cleans of second-order perturbation theory (CASPT2) with a CASSCF reference function based on an active space comprising the V-V bonding and antibonding orbitals. The results indicate the presence of a weak sigma metal-metal bond and a relatively large singlet-triplet splitting (8400 cm(-1)), with the singlet as the ground state. The computed structure for the singlet state is in agreement with experiment.
A Theoretical-study of the (cyclobutane)diazadivanadium Complex
RE, Nazzareno;
1995-01-01
Abstract
Ab initio CASSCF/CASPT2 calculations have been carried out on the V2N2H6 complex, as a model of a series of (cyclobutane)diazadivanadium complexes, in order to study the electronic structure and bonding in these complexes. Analogous calculations were performed also on the cationic and anionic species in order to study the behavior of the complexes toward oxidation and reduction. Geometry optimizations have been performed on the lowest singlet and triplet states and on the ground states of the ions, using wave functions of the restricted active space (RAS) SCF type. Dynamic correlation effects are included by cleans of second-order perturbation theory (CASPT2) with a CASSCF reference function based on an active space comprising the V-V bonding and antibonding orbitals. The results indicate the presence of a weak sigma metal-metal bond and a relatively large singlet-triplet splitting (8400 cm(-1)), with the singlet as the ground state. The computed structure for the singlet state is in agreement with experiment.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
