Journal of Physical Chemistry A, Vol.102, No.21, 3659-3667, 1998
Physical factors governing the amplitude of the electron transfer integral in mixed-valence compounds
This paper first reviews the various methods of calculation of the transfer integral in mixed valence compounds. The different physical effects affecting the electron transfer, namely overlap, through bond delocalization, relaxation and polarization of molecular orbitals, and correlation contributions are described and discussed. Illustrative model problems are proposed, and the ability of the various treatments to incorporate these physical effects is studied.
Keywords:DEDICATED CONFIGURATION-INTERACTION;NEGATIVE-DEFECT TRANSPOLYACETYLENE;BROOKER POLYMETHINECYANINE CATIONS;TRANSFER MATRIX-ELEMENTS;COUPLED-CLUSTER METHOD;CHARGE-DENSITY-WAVE;AB-INITIO;IONIZATION-POTENTIALS;EXCITATION-ENERGIES;LINEAR-RESPONSE