In mixed-valent complexes, intramolecular electron transfer can occur. This process is described by Marcus–Hush theory, in which the reactant and product are represented by two interacting parabolas on the reaction coordinate. We have developed a method that quantifies Marcus–Hush theory; more specifically, it determines the precise composition of the reaction coordinate. Our method thus provides insights into which movements of the atomic nuclei are associated with electron transfer. In many of the compounds studied so far, the barrier between the reactant and product is sufficiently narrow to make tunneling processes of heavy atoms conceivable.

Publications:

Šrut, Adam ; Lear, Benjamin J. ; Krewald, Vera (2024) Symmetric electron transfer coordinates are intrinsic to bridged systems: an ab initio treatment of the Creutz–Taube ion. In: Angewandte Chemie International Edition, 63 (31)

doi: 10.1002/anie.202404727 Artikel, Bibliographie

Šrut, Adam ; Lear, Benjamin J. ; Krewald, Vera (2023) The Marcus dimension: identifying the nuclear coordinate for electron transfer from ab initio calculations. In: Chemical Science, 14 (34)

doi: 10.1039/D3SC01402A Artikel, Bibliographie