dorsal/arxiv
View SchemaTheory of adiabatic Hexaamminecobalt-Self-Exchange
| Authors | R. G. Endres, M. X. LaBute, D. L. Cox |
|---|---|
| Categories | |
| ArXiv ID | physics/0212010 |
| URL | https://arxiv.org/abs/physics/0212010 |
| DOI | 10.1063/1.1567255 |
Abstract
We have reexamined the thermally induced Co(NH_3)_6^{2+/3+} [Co(II/III)] redox reaction using the first principles density-functional-theory method, semiclassical Marcus theory, and known charge transfer parameters. We confirm a previously suggested mechanism involving excited state (^2E_g) of Co(II) which becomes lower than the ground state (^4T_1g) in the transition state region. This lowers the transition state barrier considerably by about 6.9 kcal/mol and leads to a spin-allowed and adiabatic electron exchange process. Our calculations are consistent with previous experimental results regarding the spin-excitation energy (^3T_1g) of Co(III), and the fact that an optical absorption peak (^2E_g) of the Co(II) species could not be found experimentally. Our rate is of order 6 10^{-3} 1/Ms and hence 2 orders of magnitude faster than determined previously by experiments.
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"abstract": "We have reexamined the thermally induced Co(NH_3)_6^{2+/3+} [Co(II/III)]\nredox reaction using the first principles density-functional-theory method,\nsemiclassical Marcus theory, and known charge transfer parameters. We confirm a\npreviously suggested mechanism involving excited state (^2E_g) of Co(II) which\nbecomes lower than the ground state (^4T_1g) in the transition state region.\nThis lowers the transition state barrier considerably by about 6.9 kcal/mol and\nleads to a spin-allowed and adiabatic electron exchange process. Our\ncalculations are consistent with previous experimental results regarding the\nspin-excitation energy (^3T_1g) of Co(III), and the fact that an optical\nabsorption peak (^2E_g) of the Co(II) species could not be found\nexperimentally. Our rate is of order 6 10^{-3} 1/Ms and hence 2 orders of\nmagnitude faster than determined previously by experiments.",
"arxiv_id": "physics/0212010",
"authors": [
"R. G. Endres",
"M. X. LaBute",
"D. L. Cox"
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1063/1.1567255",
"title": "Theory of adiabatic Hexaamminecobalt-Self-Exchange",
"url": "https://arxiv.org/abs/physics/0212010"
},
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