Classification of organic molecules to obtain electron affinities from half wave reduction potentials: The aromatic hydrocarbons

Adiabatic absolute electron affinities (EA) of about 80 aromatic hydrocarbons are calculated from literature values of half wave reduction potentials in aprotic solvents. Solution energy differences are estimated by grouping the molecules based on experimental and theoretical values, chemical logic and statistical analysis. The electronegativity values, (IP+EA)/2, calculated using literature data for ionization potentials, are constant for many of the compounds. Others vary in a systematic manner, such as benzene, 4.26+/-0.05; naphthalene, 4.14+/-0.02; anthracene, 4.06+/-0.02; tetracene, 4.03+/-0.03; pentacene, 3.98+/-0.03, in eV. Theoretical values, recalculated from the beginning, compare favorably with the literature values. Three independent methods for obtaining absolute EA's are summarized and verified; the calibration of reduction potentials, the combination of ionization potentials with electronegativities and the use of semiempirical methods. (C) 1999 American Institute of Physics. [S0021-9606(99)01618-9].