ELECTRON-ATTACHMENT BY PHOSPHIRENE AND VARIOUS FLUOROMETHYL-SUBSTITUTED, CYANOMETHYL-SUBSTITUTED AND TRIFLUOROMETHYL-SUBSTITUTED PHOSPHIRENES - A THEORETICAL EXPLORATORY-STUDY

Vertical electron affinities (EA) of phosphirene and a series of vario us fluoro-, cyano- and trifluoromethyl-substituted phosphirenes have b een computed. The medium size 6-311G* basis set has been used at the MP2 level, which allows the calculation of negative EA with a satisfac tory accuracy. Most of these compounds have a negative EA ranging from -2.3 to -0.7 eV. Nevertheless, 2,3-dicyanophosphirene has a positive EA (0.32 eV) and is thus expected to yield a stable anion. The same re sult is found for the corresponding 1,2-dicyanocyclopropene. The natur e of the SOMO of title anion as a function of substituents, and the co rrelation between EA and the LUMO energy of the neutral species are di scussed.