PC2_Lesson_2 瑞士洛桑高工《光化学 II》课件.pdf

12.2 MARCUS THEORY1 Marcus classical theory The displaced harmonic oscillator (DHO) formalism and the Energy Gap Hamiltonian have been used extensively in describing charge transport reaction, such as electron and proton transfer. Rudolph A. Marcus developed an original theory to explain Here we describe the rates of electron transfer between weakly coupled donor and acceptor states the rate of ET reactions, linking the thermodynamics of the process to its kinetics. It was originally formulated to address when the potential energy depends on a nuclear coordinate, i.e., non-adiabatic electron transfer. outer sphere electron transfer reactions. These results reflect the findings of Marcus’ theory of electron transfer. His original article (1956) referred to the self exchange We can represent the problem as calculating the transfer or reaction rate for the transfer reaction in aqueous solution Fe2+ + Fe3+ → Fe3+ + Fe2+, Rudolph A. Marcus of an electron from a donor to an acceptor where the reorganization energy is solely due to (1923- ) Nobel prize 1992 D A D A (12.22) reorganization of water dipoles around solvated ions. This reaction is mediated by a nuclear coordinate q. This need not be, and generally isn’t, a simple local coordinate. For Based on statistical mechanics considerations, Marcus theory electron transfer in solution, we most commonly consider postulates that : electron transfer to progress along