dorsal/arxiv
View SchemaActivation entropy of electron transfer reactions
| Authors | Anatoli A. Milischuk, Dmitry V. Matyushov, Marshall D. Newton |
|---|---|
| Categories | |
| ArXiv ID | physics/0506107 |
| URL | https://arxiv.org/abs/physics/0506107 |
| DOI | 10.1016/j.chemphys.2005.11.037 |
Abstract
We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor-acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by continuum models is not supported by the microscopic theory. Also, the reorganization and overall solvation entropies are substantially larger in the microscopic theory compared to continuum models.
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"abstract": "We report microscopic calculations of free energies and entropies for\nintramolecular electron transfer reactions. The calculation algorithm combines\nthe atomistic geometry and charge distribution of a molecular solute obtained\nfrom quantum calculations with the microscopic polarization response of a polar\nsolvent expressed in terms of its polarization structure factors. The procedure\nis tested on a donor-acceptor complex in which ruthenium donor and cobalt\nacceptor sites are linked by a four-proline polypeptide. The reorganization\nenergies and reaction energy gaps are calculated as a function of temperature\nby using structure factors obtained from our analytical procedure and from\ncomputer simulations. Good agreement between two procedures and with direct\ncomputer simulations of the reorganization energy is achieved. The microscopic\nalgorithm is compared to the dielectric continuum calculations. We found that\nthe strong dependence of the reorganization energy on the solvent refractive\nindex predicted by continuum models is not supported by the microscopic theory.\nAlso, the reorganization and overall solvation entropies are substantially\nlarger in the microscopic theory compared to continuum models.",
"arxiv_id": "physics/0506107",
"authors": [
"Anatoli A. Milischuk",
"Dmitry V. Matyushov",
"Marshall D. Newton"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"doi": "10.1016/j.chemphys.2005.11.037",
"title": "Activation entropy of electron transfer reactions",
"url": "https://arxiv.org/abs/physics/0506107"
},
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