Charge transfer processes: the role of optimized molecular orbitals.
The influence of the molecular orbitals on charge transfer (CT) reactions is analyzed through wave function-based calculations. Characteristic CT processes in the organic radical 2,5-di-tert-butyl-6-oxophenalenoxyl linked with tetrathiafulvalene and the inorganic crystalline material LaMnO3 show that changes in the inner shells must be explicitly taken into account. Such electronic reorganization can lead to a reduction of the CT vertical transition energy up to 66%. A state-specific approach accessible through an adapted CASSCF (complete active space self-consistent field) methodology is capable of reaching good agreement with the experimental spectroscopy of CT processes. A partitioning of the relaxation energy in terms of valence- and inner-shells is offered and sheds light on their relative importance. This work paves the way to the intimate description of redox reactions using quantum chemistry methods.
Laboratoire de Chimie Quantique, Institut de Chimie - UMR 7177, Université de Strasbourg, 1 rue Blaise Pascal, 67000 Strasbourg, France. domingo@unistra.fr vrobert@unistra.fr.
Benjamin
B
Meyer
Alex
A
Domingo
Tim
T
Krah
Vincent
V
Robert