Inner‐sphere reorganization for redox pairs M(NH3)62+/3+ (M=Mn, Fe, and Co): Models and calculations

The inner-shell reorganization and activation models of the electron-transfer reactions of transition-metal hexammine complexes are presented. The inner-shell reorganization and activation energies of several hexammine redox pairs M(NH3)62+/3+ (M=Mn, Fe, and Co) in self-exchange reactions are studied by different formalisms. The extent of the anharmonicities in the vibration between the metal–ion and the ligands in the reorganization process of these complexes is determined. The inner-shell barriers of these redox pairs are dependent on reorganization model used. The contribution of the individual reactants to the inner-shell barrier is sensitive to the model used. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001

[1]  B. Brunschwig,et al.  Energy surfaces, reorganization energies, and coupling elements in electron transfer , 1999 .

[2]  Wang,et al.  Generalized gradient approximation for the exchange-correlation hole of a many-electron system. , 1996, Physical review. B, Condensed matter.

[3]  Rudolph A. Marcus,et al.  Electron transfer reactions in chemistry. Theory and experiment , 1993 .

[4]  Evert Jan Baerends,et al.  Numerical integration for polyatomic systems , 1992 .

[5]  T. Ziegler.  Approximate Density Functional Theory as a Practical Tool in Molecular Energetics and Dynamics , 1991 .

[6]  Zheng-yu Zhou,et al.  Inner-sphere reorganization energy of ions in solution: a molecular orbital calculation , 1989 .

[7]  G. te Velde,et al.  Three‐dimensional numerical integration for electronic structure calculations , 1988 .

[8]  S. Khan,et al.  Ion-dipole capture force field and its role in electron-transfer reactivity. A formalism for inner-sphere reorganization energy , 1987 .

[9]  M. Zerner,et al.  Hexaamminecobalt electron-self-exchange reaction , 1986 .

[10]  Shahed U. M. Khan,et al.  Application of ion−dipole capture models to inner-sphere reorganization energy of ions in solution , 1985 .

[11]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[12]  R. Lumry,et al.  Mechanisms of Electron Transfer , 1966 .

[13]  Rudolph A. Marcus,et al.  Chemical and Electrochemical Electron-Transfer Theory , 1964 .

[14]  Richard M. Noyes,et al.  Thermodynamics of Ion Hydration as a Measure of Effective Dielectric Properties of Water , 1962 .

[15]  Rudolph A. Marcus,et al.  On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I , 1956 .

[16]  M. Newton.  The hexaammine cobalt (2+/3+) exchange reaction: ground-state versus thermally excited pathways , 1991 .

[17]  R. D. Cannon.  Chapter 6 – Theory of electron transfer , 1980 .

[18]  N. Sutin.  Electron Exchange Reactions , 1962 .

[19]  R. Marcus.  Exchange reactions and electron transfer reactions including isotopic exchange. Theory of oxidation-reduction reactions involving electron transfer. Part 4.—A statistical-mechanical basis for treating contributions from solvent, ligands, and inert salt , 1960 .