Solvent free energies for electron transfer at a solution/metal interface. Effect of ion charge and external electric field
✍ Scribed by Daniel A. Rose; Ilan Benjamin
- Publisher
- Elsevier Science
- Year
- 1995
- Tongue
- English
- Weight
- 468 KB
- Volume
- 234
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
Solvent free energies for electron transfer reactions at the water/Pt interface are calculated using molecular dynamics umbrella sampling for different ion charges and external electric fields. In all cases, the free energy curves as a function of solvent coordinate are in reasonable agreement with the linear response approximation, with the largest deviations observed for an electron transfer involving a neutral atom. Although the metal surface in the model Hamiltonian discussed here has only a minor effect on the shape of the free energy curves, it does introduce significant correlations between inner-and outer-solvent shell fluctuations as the charge on the ion is decreased.