Artículo
Analysis of the magnetic coupling in binuclear complexes. I. Physics of the coupling
Autor/es | Jiménez Calzado, Carmen
Cabrero, Jesús Malrieu, J.P. Caballol, Rosa |
Departamento | Universidad de Sevilla. Departamento de Química Física |
Fecha de publicación | 2002 |
Fecha de depósito | 2016-10-28 |
Publicado en |
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Resumen | Accurate estimates of the magnetic coupling in binuclear complexes can be obtained from ab initio
configuration interaction ~CI! calculations using the difference dedicated CI technique. The present
paper shows that the ... Accurate estimates of the magnetic coupling in binuclear complexes can be obtained from ab initio configuration interaction ~CI! calculations using the difference dedicated CI technique. The present paper shows that the same technique also provides a way to analyze the various physical contributions to the coupling and performs numerical analysis of their respective roles on four binuclear complexes of Cu (d9) ions. The bare valence-only description ~including direct and kinetic exchange! does not result in meaningful values. The spin-polarization phenomenon cannot be neglected, its sign and amplitude depend on the system. The two leading dynamical correlation effects have an antiferromagnetic character. The first one goes through the dynamical polarization of the environment in the ionic valence bond forms ~i.e., the M1¯M2 structures!. The second one is due to the double excitations involving simultaneously single excitations between the bridging ligand and the magnetic orbitals and single excitations of the environment. This dispersive effect results in an increase of the effective hopping integral between the magnetic orbitals. Moreover, it is demonstrated to be responsible for the previously observed larger metal-ligand delocalization occurring in natural orbitals with respect to the Hartree–Fock ones |
Cita | Jiménez Calzado, C., Cabrero, J., Malrieu, J.P. y Caballol, . (2002). Analysis of the magnetic coupling in binuclear complexes. I. Physics of the coupling. Journal of Chemical Physics, 116 (7), 2728-2747. |
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