Formalisms for Electron Exchange Kinetics in Aqueous Solution, and the Role of Ab Initio Techniques in Their Implementation [electronic resource].
- Washington, D.C. : United States. Dept. of Energy, 1980.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
- Physical Description:
- 363-391 : digital, PDF file
- Additional Creators:
- Brookhaven National Laboratory
United States. Department of Energy
United States. Department of Energy. Office of Scientific and Technical Information
- Formalisms suitable for calculating the rate of electron exchange between transition metal complexes in aqueous solution are reviewed and implemented in conjunction with ab initio quantum chemical calculations which provide crucial off-diagonal Hamiltonian matrix elements as well as other relevant electronic structural data. Rate constants and activation parameters are calculated for the hex-aquo Fe<sup>2 +</sup>-Fe<sup>3+</sup> system, using a simple activated complex theory, a non-adiabatic semi-classical model which includes nuclear tunnelling, and a more detailed quantum mechanical method based on the Golden Rule. Comparisons are made between calculated results and those obtained by extrapolating experimental data to zero ionic strength. All methods yield similar values for the overall rate constant (∾ 0.1 L/(mol-sec)). The experimental activation parameters (δH<sup>‡</sup> and δS<sup>‡</sup>) are in somewhat better agreement with the semi classical and quantum mechanical results than with those from the simple activated complex theory, thereby providing some indication that non-adiabaticity and nuclear tunnelling may be important in the Fe<sup>2+/3+</sup> exchange reaction. It is concluded that a model based on direct metal-metal overlap can account for the observed reaction kinetics provided the reactants are allowed to approach well within the traditional contact distance of 6.9 Å. 6 figures, 7 tables.
- Published through SciTech Connect.
International Journal of Quantum Chemistry, Supplement: Proceedings of the International Symposium on Atomic, Molecular, and Solid-StateTheory, Collision Phenomena, Quantum Statistics, and Computational Methods 18 S14
International Symposium on Atomic, Molecular, and Solid-State Theory, Flagler Beach, FL, USA, 10-14 Mar 1980.
Newton, M. D.
- Funding Information:
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