Abstract
Extensive CI calculations have been done on free base porphin and the metallo derivative of porphin, tetrazaporphin, phthalocyanine, various benzporphins, chlorin, and bacteriochlorin. The transition gradient operator gives good agreement with experimental intensities. Free base porphin may have a weakπ-π * transition around 480nm. Tetrabenzporphin and phthalocyanine are predicted to have much more intensity around 50000 cm−1 than porphin and tetrazaporphin due to benzenoid transitions, a prediction borne out by the available data. Magnetic effects are calculated for the low energy excited states. Q state angular momentum is calculated to be 4.35ħ for porphin and 3.13h for phthalocyanine. Although these numbers agree with some experimental results, the calculations show that the experimental analysis needs further refinement.
Zusammenfassung
Es wurden ausführliche CI-Rechnungen für die freie Porphinbase und die Metallderivate von Porphin, Tetrazaporphin, Phthalocyanin, verschiedene Benzporphine, Chlorin und Bacteriochlorin durchgeführt. Der Operator des Übergangsgradienten zeigt gute Übereinstimmung mit experimentellen Intensitäten. Die freie Base Porphin hat höchstwahrscheinlich bei 480nm einen schwachenπ-π *-Übergang. Mit Hilfe der vorhandenen Daten ist die Voraussage möglich, daß die benzoloiden Banden im Bereich um 50000 cm−1 im Falle von Tetrabenzporphin und Phthalocyanin intensiver als bei Porphin und Tetrazaporphin sind. Ferner werden die magnetischen Eigenschaften für angeregte Zustände niedriger Energie berechnet. Man erhält den Drehimpuls des Q-Zustandes zu 4,35ħ für Porphin und 3,13ħ für Phthalocyanin. Obwohl diese Werte mit einigen experimentellen Resultaten übereinstimmen, zeigen die Rechnungen, daß die experimentelle Analyse weiterer Verfeinerung bedarf.
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McHugh, A.J., Gouterman, M. & Weiss, C. Porphyrins XXIV. Energy, oscillator strength, and Zeeman splitting calculations (SCMO-CI) for phthalocyanine, porphyrins, and related ring systems. Theoret. Chim. Acta 24, 346–370 (1972). https://doi.org/10.1007/BF01007552
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DOI: https://doi.org/10.1007/BF01007552