Monte Carlo simulation study on reorganization energy of electron-transfer reactions in polar solution

The Rehm–Weller Experiment in View of Distant Electron Transfer

“…The parameter d was set to 10.5 Å eV, giving rise to 61 % of the contact value if Marcus theory was applied, which is in good agreement with previous observations 58. 59…”

“…Monte Carlo simulations have shown that the classical Marcus expression does not only overestimate l(s), but also results in a different distance dependence. [58] Henceforth we will use an approximation for l(r) [Eq. (18)] similar to the one which has already been successfully applied by Matsuda et al [16] lðrÞ…”

“…The parameter d was set to 10.5 eV, giving rise to 61 % of the contact value if Marcus theory was applied, which is in good agreement with previous observations. [58,59] Results and Discussion Figure 2 shows the steady-state quenching rate dependence on the reaction free energy for several experimental data sets (see also Table 1). Besides the data obtained in this study, we have included Rehms and Wellers original data [1] and a representative study by Niwa et al [60] Niwas data spans a range of more than 2.5 eV.…”

“…Monte Carlo simulations have shown that the classical Marcus expression does not only overestimate λ ( σ ), but also results in a different distance dependence 58. Henceforth we will use an approximation for λ ( r ) [Eq.…”

A molecularly based theory for electron transfer reorganization energy

“…17,18,[21][22][23][24][25][26][27][28][29][30] However, multiple long trajectories are required to perform umbrella sampling, making it impractical to perform calculations for general solvents. Integral-equation theories [31][32][33][34][35][36][37][38] are a more convenient alternative to the laborious nonequilibrium sampling schemes in MD simulations, but nanosecond MD simulations are still required to compute the solvent correlation functions in these approaches.…”