Marcus’ electron transfer rate revisited via a Rice-Ramsperger-Kassel-Marcus analogue: A unified formalism for linear and nonlinear solvation scenarios
نویسندگان
چکیده
In the pioneering work by R. A. Marcus, solvation effect on electron transfer (ET) processes was investigated, giving rise to celebrated nonadiabatic ET rate formula. this work, basis of thermodynamic potentials analysis, we reexamine Marcus' formula with respect Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Interestingly, obtained RRKM analogue, which recovers original that is in a linear scenario, also applicable nonlinear scenarios, where multiple curve{crossing exists. Parallelly, revisit corresponding Fermi's golden rule results, some critical comments against analogue proposed work. For illustration, consider quadratic physically well-supported descriptors.
منابع مشابه
A8...—a non-Rice–Ramsperger–Kassel–Marcus system?
Crossed molecular beam experiments were conducted to investigate the reaction of ground state carbon atoms, C(P j), with 1,2-butadiene, H2CCCH~CH3! (X A8), at three collision energies of 20.4 kJ mol, 37.9 kJ mol, and 48.6 kJ mol. Ab initio calculations together with our experimental data reveal that the reaction is initiated by a barrier-less addition of the carbon atom to the p system of the 1...
متن کاملSolvent dynamics: Modified Rice–Ramsperger–Kassel–Marcus theory. II. Vibrationally assisted case
Expressions are given for a solvent dynamics-modified Rice–Ramsperger–Kassel–Marcus ~RRKM! theory for clusters. The role of vibrational assistance across the transition state region is included. The usual differential equation for motion along the slow coordinate X in constant temperature systems is modified so as to apply to microcanonical systems. A negative entropy term, 2Sv(X), replaces the...
متن کاملImproved Whitten-Rabinovitch approximation for the Rice-Ramsperger-Kassel-Marcus calculation of unimolecular reaction rate constants for proteins.
The Whitten-Rabinovitch (WR) approximation used in the semi-classical calculation of the Rice-Ramsperger-Kassel-Marcus (RRKM) unimolecular reaction rate constant was improved for reliable application to protein reactions. The state sum data for the 10-mer of each amino acid calculated by the accurate Beyer-Swinehart (BS) algorithm were used to obtain the residue-specific correction functions (w...
متن کاملA combined crossed-beam, ab initio, and Rice–Ramsperger–Kassel– Marcus investigation of the reaction of carbon atoms
The reactions of atomic carbon, C(P j), with benzene, C6H6(X A1g), and with d6-benzene, C6D6(X A1g) were investigated at twelve collision energies between 8.8 and 52.5 kJ mol 21 using the crossed molecular beams technique. Forward-convolution fitting of the data, high-level electronic structure calculations, and Rice–Ramsperger–Kassel–Marcus ~RRKM! investigations on the singlet and triplet C7H6...
متن کاملAnharmonic Rice-Ramsperger-Kassel-Marcus (RRKM) and product branching ratio calculations for the partially deuterated protonated water dimers: dissociation and isomerization.
Partially deuterated protonated water dimers, H2O·H(+)·D2O, H2O·D(+)·HDO, and HDO·H(+)·HDO, as important intermediates of isotopic labeled reaction of H3O(+) + D2O, undergo direct dissociation and indirect dissociation, i.e., isomerization before the dissociation. With Rice-Ramsperger-Kassel-Marcus theory and ab initio calculations, we have computed their dissociation and isomerization rate con...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Chinese Journal of Chemical Physics
سال: 2021
ISSN: ['2327-2244', '1674-0068']
DOI: https://doi.org/10.1063/1674-0068/cjcp2101004