Valence ionization potentials and cation radicals of prototype porphyrins. The remarkable performance of nonlocal density functional theory

Abstract

Nonlocal density functional theory (NLDFT) has been used to calculate the lower ionized states of the free-base forms of porphin, bacteriochlorin, and porphyrazine and also zinc porphin. For porphin, the calculated vertical ionization potentials (IPs) quantitatively reproduce the low-energy end of the experimental gas-phase ultraviolet photoelectron spectrum, which suggests that NLDFT could be an exceptionally useful tool for studying IPs and cation radical states of a variety of porphyrinic materials.