Abstract
The correlations of the observed ionization potentials and electron affinities with the orbital energies of SCF-MO's calculated by the variable-β modification of the Pariser-Parr-Pople method were examined for 30 conjugated molecules including heterocycles. A simple linear relation has been found between the ionization potential and the energy of the highest occupied SCF-MO as well as between the electron affinity and the energy of the lowest vacant SCF-MO. The ionization potential and electron affinity are estimated by using these empirical relations for 24 conjugated heteromolecules of biochemical interest.
Zusammenfassung
PPP-Rechnungen nach der variablesβ-Methode an 30 carbo- und heterocyclischenπ-Systemen zeigen eine gute Korrelation der experimentellen ionisationspotentiale und Elektronenaffinitäten mit den Energien der höchsten besetzten bzw. tiefsten unbesetzten SCF-MOs. Die so erhaltenen Regressionsgeraden wurden zur Bestimmung vos Ionisationspotentialen und Elektronenaffinitäten vos 24 biochemisch interessanten Heterosystemen herangezogen.
Résumé
Examen pour 30 molécules conjuguées des corrélations entre potentiels d'ionisation et affinités électroniques expérimentales avec les énergies des orbitales moléculaires SCF de la méthode de Pariser-Parr-Pople àβ variable. Une relation linéaire simple a été trouvée entre le potentiel d'ionisation et l'énergie de la plus haute orbitale moléculaire occupée ainsi qu'entre l'affinité électronique et l'énergie de la plus basse orbitale vacante. Ces relations empiriques permettent d'estimer les potentiels d'ionisation et l'affinité électronique de 24 molécules conjugées d'intérêt biochimique.
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Kunii, T.L., Kuroda, H. Ionization potentials and electron affinities of carbo- and heterocyclicπ-conjugated molecules. Theoret. Chim. Acta 11, 97–106 (1968). https://doi.org/10.1007/BF01184316
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DOI: https://doi.org/10.1007/BF01184316