Event Information
QM/MM Calculations of Electron Transfer Reactions: Fractional Number of Electrons Approach
- Abstract:
Electron transfer (ET) process is of fundamental importance in both chemistry and biology. However, the theoretical study of the ET process is challenging because of the quantum eŽect in the solute and complicated behavior of solvent. To address the need for detailed understandings of ET process at molecular level, we developed a new approach that combines the fractional-electron DFT calculation with the QM/MM method to calculate the redox free energy of ET reactions in solution. The hexaaquo iron[II/III] and ruthenium[II/III] complexes, are examined here. The calculated oxidation free energy are 5.82eV(Fe[II/III]) and 5.11eV(Ru[II/III]), agree well with experimental data 5.50eV(Fe[II/III]) and 4.96eV(Ru[II/III]), respectively. Furthermore, the diabatic free energy surfaces are reconstructed by the weighted histogram analysis method. The reorganization energy and the diabatic activation energy show good agreement with experimental data. The calculation results validate the applications of the new ab initio QM/MM approach to free energy calculations and suggests extensions to more complex systems.
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