The ethylene/metal(0) and ethylene/metal(I) redox system: model ab initio calculations |
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Authors: | Alexander Alex Elke Hänsele Timothy Clark |
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Affiliation: | (1) Medicinal Informatics, Structure and Design, Pfizer Global Research and Development, Sandwich Laboratories, Ramsgate Road, Sandwich, CT13 9NJ, UK;(2) Computer-Chemie-Centrum der Universitaet Erlangen-Nuernberg, Naegelsbachstrasse 25, 91052 Erlangen, Germany |
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Abstract: | Ab initio calculations (coupled cluster with single and double excitations; CCSD) have been used to investigate the model redox systems ethylene:M(0) (M = Li, Na, K, Rb, Cs) and ethylene:M(I) (M = Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg). Within C2v symmetry, the ground (2A1) states correspond to the charge distribution given in the title. The lowest (2B2) excited states correspond, somewhat counter intuitively, to the ethylene*-/=M(II)ion pair. These trends can be rationalized on the basis of simple electrostatic and configuration-mixing arguments that lead to two simple equations for predicting the electron-transfer energies for oxidation or reduction of the ethylene. The electron-transfer energies to the 2B2 ion pairs are dominated by the electrostatic ion-pairing energies. |
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Keywords: | Electron transfer Ab initio CCSD(T) Ethylene |
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