Molecular dynamics simulations of solvent reorganization in electron-transfer reactions
10.1063/1.1408295
Crossref journal-article
AIP Publishing
The Journal of Chemical Physics (317)
Abstract

We present molecular dynamics simulations of solvent reorganization in electron-transfer reactions in water. Studying a series of solutes with the same core radius (typical for chlorine) but with varying charge from −3 to +3, the simulations show that the single-solute solvent reorganization energy depends quite strongly on the solute’s charge, in contrast with the continuum Marcus theory. Due to the ion-dipole interactions, electrostriction plays an important role for charged species. The effective radius of a neutral species is comparatively larger, making the solvent reorganization energy small. Strong increases in the solvent reorganization energy occur when the solute is charged to either −1 to +1, due to the significantly smaller effective radius caused by the ion-dipole interactions. However, the effect is nonsymmetric because the center of the water dipole can approach closer to the negative species than to the positive species. Hence, the nonlinearity occurs mainly in the transition from 0 to –1. For higher charges (+3, +2, −2, −3), dielectric saturation causes a decrease in the reorganization energy with increasing charge. We also calculate the equilibrium activation energy for an outer-sphere electrochemical electron-transfer reaction of the X+e−⇌X− type, with varying of the core radius of the X species. The deviations from Marcus theory are relatively small for large reactants, but get more significant for small reactants. This is mainly due to the fact that the changes in electrostriction have a comparatively large effect for small solutes.

Bibliography

Hartnig, C., & Koper, M. T. M. (2001). Molecular dynamics simulations of solvent reorganization in electron-transfer reactions. The Journal of Chemical Physics, 115(18), 8540–8546.

Authors 2
  1. Christoph Hartnig (first)
  2. Marc T. M. Koper (additional)
References 41 Referenced 72
  1. 10.1063/1.1742723 / J. Chem. Phys. (1956)
  2. 10.1063/1.1696792 / J. Chem. Phys. (1965)
  3. 10.1002/anie.199311113 / Angew. Chem. Int. Ed. Engl. (1993)
  4. {'key': '2024021108594251500_r4', 'first-page': '249', 'volume': '4', 'year': '1966', 'journal-title': 'Adv. Electrochem. Electrochem. Eng.'} / Adv. Electrochem. Electrochem. Eng. (1966)
  5. 10.1021/j100209a016 / J. Phys. Chem. (1982)
  6. 10.1021/ja00237a013 / J. Am. Chem. Soc. (1987)
  7. 10.1063/1.459255 / J. Chem. Phys. (1990)
  8. 10.1063/1.454929 / J. Chem. Phys. (1988)
  9. 10.1063/1.459596 / J. Chem. Phys. (1990)
  10. 10.1063/1.455649 / J. Chem. Phys. (1988)
  11. 10.1063/1.459932 / J. Chem. Phys. (1991)
  12. 10.1021/j100343a002 / J. Phys. Chem. (1989)
  13. 10.1021/j100189a032 / J. Phys. Chem. (1992)
  14. 10.1021/jp970081u / J. Phys. Chem. B (1997)
  15. 10.1021/j100131a003 / J. Phys. Chem. (1993)
  16. 10.1063/1.469431 / J. Chem. Phys. (1995)
  17. {'key': '2024021108594251500_r17', 'first-page': '106746', 'volume': '100', 'year': '1996', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1996)
  18. 10.1016/S0022-0728(97)00644-X / J. Electroanal. Chem. (1998)
  19. {'key': '2024021108594251500_r19', 'first-page': '3442', 'volume': '103', 'year': '1999', 'journal-title': 'J. Phys. Chem. B'} / J. Phys. Chem. B (1999)
  20. 10.1016/S0009-2614(99)00353-X / Chem. Phys. Lett. (1999)
  21. {'key': '2024021108594251500_r21', 'first-page': '3545', 'volume': '100', 'year': '1993', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1993)
  22. 10.1016/0009-2614(95)00014-U / Chem. Phys. Lett. (1995)
  23. 10.1063/1.467841 / J. Chem. Phys. (1994)
  24. 10.1063/1.478557 / J. Chem. Phys. (1999)
  25. 10.1039/DF9602900021 / Discuss. Faraday Soc. (1960)
  26. 10.1021/j100308a040 / J. Phys. Chem. (1987)
  27. 10.1021/j100124a023 / J. Phys. Chem. (1993)
  28. 10.1063/1.470232 / J. Chem. Phys. (1995)
  29. 10.1063/1.471268 / J. Chem. Phys. (1996)
  30. 10.1063/1.471465 / J. Chem. Phys. (1996)
  31. 10.1016/S0013-4686(97)00083-2 / Electrochim. Acta (1997)
  32. 10.1016/S1388-2481(99)00087-9 / Electrochem. Commun. (1999)
  33. 10.1063/1.1289886 / J. Chem. Phys. (2000)
  34. 10.1021/j100308a038 / J. Phys. Chem. (1987)
  35. 10.1021/jp953050c / J. Phys. Chem. (1996)
  36. 10.1063/1.469431 / J. Chem. Phys. (1995)
  37. 10.1063/1.478698 / J. Chem. Phys. (1999)
  38. 10.1021/j100357a005 / J. Phys. Chem. (1989)
  39. 10.1021/j100277a019 / J. Phys. Chem. (1986)
  40. 10.1021/jp980210m / J. Phys. Chem. B (1998)
  41. 10.1016/S0301-0104(00)00115-4 / Chem. Phys. (2000)
Dates
Type When
Created 23 years, 1 month ago (July 26, 2002, 9:27 a.m.)
Deposited 1 year, 6 months ago (Feb. 11, 2024, 4 a.m.)
Indexed 3 weeks, 5 days ago (Aug. 6, 2025, 10 a.m.)
Issued 23 years, 9 months ago (Nov. 8, 2001)
Published 23 years, 9 months ago (Nov. 8, 2001)
Published Print 23 years, 9 months ago (Nov. 8, 2001)
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@article{Hartnig_2001, title={Molecular dynamics simulations of solvent reorganization in electron-transfer reactions}, volume={115}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1408295}, DOI={10.1063/1.1408295}, number={18}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Hartnig, Christoph and Koper, Marc T. M.}, year={2001}, month=nov, pages={8540–8546} }