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LCAO-MO-SCF-CI semi-empirical π-electron calculations on heteroaromatic systems

I. Hydroxy aromatic compounds

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Abstract

The electronic spectra and structure for phenol, the three dihydroxybenzene isomers, and α- and β-naphthol have been calculated using a modification of the Pariser-Parr-Pople method. Core integrals are defined to be essentially independent of geometry and orthogonalized atomic orbitals are used. The electronic transitions considered involve singlet-singlet and triplet-triplet π→π * excitations. A limited configuration interaction has been included, involving either single electron excitations or both single and double electron excitations between the two highest occupied and the two lowest unoccupied molecular orbitals. Agreement between calculated and experimental values is good, and calculated values for oscillator strengths are considerably improved when double electron excitations are admitted.

Zusammenfassung

Die Elektronenspektren und Struktur von Phenol, den drei Isomeren des Dihydroxybenzols und α- und β-Naphthol wurden mit einer Modifikation der PPP-Methode berechnet. Die Rumpfintegrale werden so definiert, daß sie im wesentlichen unabhängig von der Geometrie sind; es werden orthogonalisierte Atomorbitale benutzt. Die betrachteten Elektronenübergänge enthalten Singulett-Singulett- und Triplett-Triplett-π→π *-Übergänge. Es wurde eine begrenzte Konfigurationswechselwirkung eingeschlossen, die nur Einelektronen- oder Ein- und Zweielektronenanregung zwischen den beiden höchsten besetzten und den beiden niedrigsten unbesetzten MO's enthält. Es besteht gute Übereinstimmung von berechneten und experimentellen Daten. Die berechneten Werte für Oszillatorenstärken werden erheblich verbessert, wenn man Zweielektronenanregung einbezieht.

Résumé

Les spectres électroniques et les structures du phénol, des trois dihydroxybenzènes isomères, de l'α et du β naphtol ont été calculé pour une variante de la méthode de Pariser-Parr-Pople. Les intégrales de coeur sont définies de manière à être indépendantes de la géométrie et des orbitales atomiques orthogonalisées sont employées. On considère les transitions électroniques π→π * singulet-singulet et triplet-triplet. Une interaction de configuration limitée a été effectuée en considérant soit des minoexcitations soit des mono et des diexcitations de la plus haute orbitale occupée aux deux orbitales libres les plus basses. L'accord entre les valeurs calculées et les valeurs expérimentales est bon, et les valeurs calculées des forces oscillatrices sont considérablement améliorées lorsque l'on tient compte des états diexcités.

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Author notes

  1. Br. Jerome D. Wegener

    Present address: Christian Brothers College, Memphis, Tenn.

Authors and Affiliations

  1. Dept. of Chemistry, Duquesne University, Pittsburgh, Pa.

    G. W. Pukanic, D. R. Forshey, Br. Jerome D. Wegener & J. B. Greenshields

Authors
  1. G. W. Pukanic
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  2. D. R. Forshey
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  3. Br. Jerome D. Wegener
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  4. J. B. Greenshields
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Additional information

This investigation was supported by a National Science Foundation grant, No. GB-4065. Abstracted in part from the Ph. D. thesis of G. W. Pukanic, Duquesne University, 1967.

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Pukanic, G.W., Forshey, D.R., Wegener, B.J.D. et al. LCAO-MO-SCF-CI semi-empirical π-electron calculations on heteroaromatic systems. Theoret. Chim. Acta 9, 38–50 (1967). https://doi.org/10.1007/BF00526107

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