title: The ethylene/metal(0) and ethylene/metal(I) redox system: model ab initio calculations.
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.
authors.affiliation: Medicinal Informatics, Structure and Design, Pfizer Global Research and Development, Sandwich Laboratories, Ramsgate Road, Sandwich, CT13 9NJ, UK.
authors.forename: Alexander
authors.initials: A
authors.lastname: Alex
authors.forename: Elke
authors.initials: E
authors.lastname: Hänsele
authors.forename: Timothy
authors.initials: T
authors.lastname: Clark
mesh_terms: D001895:Boron / Q000737:chemistry; D003198:Computer Simulation; D005030:Ethylenes / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D008670:Metals / Q000737:chemistry*; D008956:Models, Chemical; D010084:Oxidation-Reduction; D014732:Vibration
chemical_list: D005030:Ethylenes; D007477:Ions; D008670:Metals; C036216:ethylene; D001895:Boron