Abstract
Using the CNDO/S method, we have performed quantum‐chemical calculations of the ground and excited electronic states of porphin molecules (symmetry D 2h ) and a number of porphin isomers: porphycene (C2h ), hemiporphycene, corphycene (C2v ), isoporphycene, and three nonsynthesized structural isomers of the porphin skeleton by its bridge groups —(CH) meso —. The results of the calculations are compared with the corresponding data for the free‐base porphin molecule (H2P). Near the boundary between the occupied and vacant orbitals the isomers form rows of single‐electron levels with similar energy characteristics. For the MOs of these isomers, the H2P MOs closest in distribution on the “comparable” atomic centers are given. The weak (Q) and strong (B) transitions in the visible and near UV regions point to the porphyrin type of spectra of all the isomers. The calculation data on the excited electronic states of N‐, g‐, and nπ‐type H2P near and above the B states are given; the presence of such states in other isomers is shown. The calculation does not point to a difference in the position of the first singlet transitions in the first five isomers. The calculation data on the lower singlet‐triplet transitions are also reported.
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Gael', V.I. Calculation of Quantum‐Chemical Characteristics of the Ground and Excited Electronic States of Porphin and Its Tetrapyrrole Isomers. Journal of Applied Spectroscopy 68, 267–279 (2001). https://doi.org/10.1023/A:1019268219840
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DOI: https://doi.org/10.1023/A:1019268219840