Biomimetic trinuclear copper mixed valence systems: electronic and magnetic parameters from ab initio calculations

Carmen J. Calzado (1)

1 Departamento de Quimica Fisica

A series of ab initio quantum chemistry calculations on a trinuclear mixed-valence system [(NH3)6Cu3O2]+3 have been performed in order to simultaneously evaluate its magnetic and electronic parameters, namely the magnetic coupling constants J1 and J2, the electron transfer integrals t1 and t2, and the exchange-transfer terms h1 and h2. The procedure is based on the use of the effective Hamiltonian theory. The results evidence the presence of two ferromagnetic interactions in this compound, in good agreement with the behaviour found in the real system [L3Cu3O2]+3, where L= N-permethyl-(1R,2R)-cyclohexenediamine. Regarding electron transfer terms, their values are about one order larger than the corresponding magnetic coupling constants, and essentially controlled by the direct interactions through the Cu d orbitals. The exchange-transfer terms are non negligible, their amplitudes being similar to the J1 constant.

Mots clés: Physical Sciences

Carmen J. Calzado. Biomimetic trinuclear copper mixed valence systems: electronic and magnetic parameters from ab initio calculations. Molecular Simulation, 2009, 35 (12-13), pp.1057-1066. ⟨10.1080/08927020902859074⟩. ⟨hal-00515083⟩