Computational methods for intramolecular electron transfer in a ferrous-ferric iron complex
The limitations of common theoretical and molecular computational approaches for predicting electron transfer quantities were assessed, using an archetypal bridged ferrous-ferric electron transfer system in aqueous solution. The basis set effect on the magnitude of the electronic coupling matrix element computed using the quasi-diabatic method was carefully examined, and it was found that the error related to a poor basis set could exceed the thermal energy at room temperature. A range of approaches to determining the external (solvent) reorganization energy were also investigated. Significant improvements from the Marcus continuum model can be obtained by including dipolar Born-Kirkwood-Onsager correction. In this regard we also found that Klamt’s Conductor-Like Screening Model (COSMO) yields estimations of the external reorganization energy similar to those obtained with explicit solvent molecular dynamics simulations, if the fast-frequency modes are neglected, which makes it an attractive alternative to laborious umbrella sampling simulations. As expected, dielectric saturation observed in the first solvation shell decreases the curvature of the potential energy surface, but it nonetheless remains a quadratic function of the reaction coordinate. The linearity of solvent response to the charge redistribution was assessed by analyzing the energy gap autocorrelation function as well as the solvent density and dipole moment fluctuations. Molecular dynamics was also used to evaluate the sign and magnitude of the solvent reorganization entropy, to determine its effect on the predicted electron transfer rate. Finally, we present a simple way of estimating the vibration frequency along the reaction coordinate, which also enables prediction of the mass dependent isotopic signature of electron-transfer reactions.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1021278
- Report Number(s):
- PNNL-SA-70607; 25629; KC0303020; TRN: US201116%%1161
- Journal Information:
- Journal of Colloid and Interface Science, 361(1):293-306, Vol. 361, Issue 1; ISSN 0021-9797
- Country of Publication:
- United States
- Language:
- English
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