2020/12/31 by Yao Wang, Yu Su, Rui‐Xue Xu +3
Chemistry · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Chemistry #Computational chemistry #Electron transfer #Fermi Gamma-ray Space Telescope #Fermi's golden rule #Kinetics #Marcus theory #Molecule #Nonlinear system #Photochemistry and Electron Transfer Studies #Physical chemistry #Physics #Quantum mechanics #Reaction rate constant #Solvation #Spectroscopy and Quantum Chemical Studies #Statistical physics #Work (physics) #physics.chem-ph
paper · pdf · doi:10.1063/1674-0068/cjcp2101004
published as Chin. J. Chem. Phys. 34(4), 462 (2021) · 7 pages, 2 figures
arxiv created 2021/04/14 · openalex created_date 2021/04/26 · openalex publication_date 2021/06/02 · arxiv updated 2021/11/19 · openalex updated_date 2026/08/05
In the pioneering work by R. A. Marcus, the solvation effect on electron transfer (ET) processes was investigated, giving rise to the celebrated nonadiabatic ET rate formula. In this work, on the basis of the thermodynamic solvation potentials analysis, we reexamine Marcus’ formula with respect to the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Interestingly, the obtained RRKM analogue, which recovers the original Marcus’ rate that is in a linear solvation scenario, is also applicable to the nonlinear solvation scenarios, where the multiple curve-crossing of solvation potentials exists. Parallelly, we revisit the corresponding Fermi’s golden rule results, with some critical comments against the RRKM analogue proposed in this work. For illustration, we consider the quadratic solvation scenarios, on the basis of physically well-supported descriptors.