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تسجيل مستخدم جديدMarcus electron transfer rate revisited via a Rice-Ramsperger-Kassel-Marcus analogue: A unified formalism for linear and nonlinear solvation scenarios
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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 Fermis 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.
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We examine electron transfer between two quantum states in the presence of a dissipative environment represented as a set of independent harmonic oscillators. For this simple model, the Marcus transfer rates can be derived and we show that these rate
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Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions. If such e
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Marcus-Levich-Jortner (MLJ) theory is one of the most commonly used methods for including nuclear quantum effects into the calculation of electron-transfer rates and for interpreting experimental data. It divides the molecular problem into a subsyste
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The effect of solvation on the electron transfer (ET) rate processes is investigated on the basis of the exact theory constructed in J. Phys. Chem. B Vol. 110, (2006); quant-ph/0604071. The nature of solvation is studied in a close relation with the
mechanism of ET processes. The resulting Kramers turnover and Marcus inversion characteristics are analyzed accordingly. The classical picture of solvation is found to be invalid when the solvent longitudinal relaxation time is short compared with the inverse temperature.
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