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| - Dedicated Molecular Orbitals for the Variational Determination of the Electron-TransferMatrix Element. Method and Application to a Cu(I)−Cu(II) Mixed Valence Compound
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| - A method to obtain molecular orbitals specially suited for thevariational calculation of the electron-transfermatrix element Vab is reported. Theseelectron-transfer dedicated molecular orbitals (ET-DMOs) aredeterminedfrom the diagrammatic second-order expansion of the transfer integralHab and are associated to aparticipationindex which allows for a truncation of the molecular orbital basis setand, therefore, for a reduction of thevariational space in a difference-dedicated configuration interaction(DDCI) calculation. The suitability ofthese ET-DMOs is first tested with some simple organic models for whicha reduction of the second-orderspace of 40−60% is possible without significant loss of precision.The calculation of the transfer integral fora Cu(I)−Cu(II) mixed-valence system is also reported.Using as model a cluster of formulaCu2Cl63-,Hab isestimated to be 2000 cm-1 from aperturbational-variational calculation. The stability of theET-DMOs forthis system is found to be excellent allowing for a reduction of thevariational space of 76% with a relativeerror of only 0.15%.
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