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Semiempirical molecular orbital studies of phthalocyanines

I. The electronic structure and excited states of phthalocyanine, H2Pc

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Abstract

Theπ andσ lone pair electron system of the phthalocyanine molecule has been studied by a semiempirical SCF-MO method. Electronic transitions of bothπ-π * andn-π * types have been considered. The excited states have been calculated by means of the method of superposition of configurations where all singly excited states are included. Assignments for the electronic spectrum of phthalocyanine could be made in good agreement with experiment. The position of the lowest electronically allowedn-π * transition is predicted to be found in the region of the strong Soret band.

Zusammenfassung

Das Elektronensystem der einsamenπ- undσ-Elektronenpaare des Phthalocyaninmoleküls wurde mit Hilfe einer semiempirischen SCF-MO-Methode untersucht. Dabei wurden Elektronen-übergänge vomπ-π *-Typ und vomn-π *-Typ behandelt. Die angeregten Zustände wurden nach der CI-Methode unter Einschluß aller einfach angeregten Zustände berechnet. Die Zuordnung der Ergebnisse zum Elektronenspektrum des Phthalocyanins brachte gute Übereinstimmung mit dem Experiment. Die Lage des niedrigsten elektronisch erlaubtenn-π *-Übergangs wird für das Gebiet der starken Soret-Bande vorhergesagt.

Résumé

Les électronsπ et les paires libresσ de la molécule de phthalocyanine ont été étudiés par une méthode SCF MO semi-empirique. On envisage les transitions du typeππ * etn-π *. Les états excités ont été calculés par la méthode de superposition des configurations incluant tous les états monoexcités. Les attributions du spectre électronique de la phthalocyanine sont en bon accord avec l'expérience. La position de la plus basse transition permise du typen-π * est prédite dans la région de la forte bande de Soret.

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Author notes

  1. A. Henriksson

    Present address: Department of Physical Chemistry, University of Helsinki, Meritullink. 1, Helsinki 17

Authors and Affiliations

  1. Institute of Theoretical Physics, University of Stockholm, Vanadisvägen 9, 113 46, Stockholm, Sweden

    A. Henriksson & M. Sundbom

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  1. A. Henriksson
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  2. M. Sundbom
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Henriksson, A., Sundbom, M. Semiempirical molecular orbital studies of phthalocyanines. Theoret. Chim. Acta 27, 213–222 (1972). https://doi.org/10.1007/BF01046366

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