Theoretical investigations of the electronic states of porphyrins. II. Normal and hyper phosphorus porphyrins

Ab initio methods have been used to calculate the ground and excited states of “normal” and “hyper” porphyrins. Perturbation theory and CI methods were used to determine differential ground and excited‐state correlation effects for [P v (P)F 2 ] + and [P III (P)] + . A comparison is made to the INDO / S / CI predicted wavefunctions and spectra and to the experimental spectra of closely related molecules. The “hyper” [P III (P)] + calculations show some very low energy electronic transitions which provide an explanation for an anomalous “red” band in the spectrum and for the lack of fluorescence. Ab initio calculations also predict that (1) the lowest energy 1 A 1 state is a two‐configuration wavefunction which can be described as a diradical, (2) the two lowest‐energy singlet excited states are double excitations from the closed shell SCF configuration, and (3) a 3 B 2 state is very close in energy to the lowest 1 A 1 state.