Rauhut G, Clark T (1993)
Publication Status: Published
Publication Type: Journal article
Publication year: 1993
Publisher: American Chemical Society
Book Volume: 115
Pages Range: 9127-9135
Journal Issue: 20
DOI: 10.1021/ja00073a031
AM1 and HF/6-31G* molecular orbital calculations have been used to investigate the electron self-exchange reactions between a series of substituted 1,4-diaminobenzenes and their radical cations. Comparisons with known experimental data and the results of the ab initio calculations suggest that AM1 performs well for this problem. The internal reorganization energy, lambda(i), has been estimated from the differences between the vertical and adiabatic ionization potentials of the neutral compounds and the corresponding electron affinities of the radical cations and is found to be significantly larger than previous estimates. Direct CI calculations of lambda for the radical cation/neutral molecule complex reveal that stabilization of the ground state (complexation) and the corresponding destabilization of the first excited state increase lambda further. There is, however, a large zero-point energy contribution that lowers the classical electron-transfer activation energy significantly. The calculated thermodynamics of the classical activation process are in good agreement with experiment.
APA:
Rauhut, G., & Clark, T. (1993). ELECTRON-TRANSFER REACTIONS - AM1 AND AB-INITIO STUDIES ON SELF-EXCHANGE IN P-DIAMINOBENZENE SYSTEMS. Journal of the American Chemical Society, 115(20), 9127-9135. https://doi.org/10.1021/ja00073a031
MLA:
Rauhut, Guntram, and Timothy Clark. "ELECTRON-TRANSFER REACTIONS - AM1 AND AB-INITIO STUDIES ON SELF-EXCHANGE IN P-DIAMINOBENZENE SYSTEMS." Journal of the American Chemical Society 115.20 (1993): 9127-9135.
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