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Quantenmechanische Untersuchung absoluter Ramanintensitäten

Quantum mechanical studies of absolute raman intensities (application to symmetrical stretching modes in some molecules and ions)

Anwendung auf symmetrische Streckschwingungen bei einigen Molekülen und Ionen

  • Anorganische, Struktur- und Physikalische Chemie
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Abstract

Absolute intensity of a Raman line which is proportional to the square of the derivative of molecular polarizability has been determined from the delta-function potential model yielding theR 4-dependence of the bond parallel component of the polarizability. The delta-function potential model has been used to derive the expression for the derivative of the mean molecular polarizability with respect to a change in the internuclear distance at the equilibrium configuration for many diatomic molecules, and for the symmetrical stretching modes of many polyatomic molecules and ions in the ground electronic state. The computed polarizability derivatives are in good agreement with most of the experimental ones derived from Raman intensities. Bond orders have been computed from the experimental polarizability derivatives for various ionic systems through the use of the delta-function potential model, and the results have been discussed in relation to the contributions of the π and σ electrons to the polarizability derivatives of multiple bonds.

Zusammenfassung

Ausgehend vom Deltafunktionspotentialmodell wurde die absolute Intensität einer Ramanlinie, die dem Quadrat der molekularen Polarisierbarkeit proportional ist, bestimmt. Auf Grund des Deltafunktionspotentialmodells ergibt sich eine Abhängigkeit der Komponente der Polarisierbarkeit in der Bindungsrichtung vonR 4. Wir leiteten aus dem Deltafunktionspotentialmodell einen Ausdruck für die Ableitung der mittleren molekularen Polarisierbarkeit nach der Entfernung der Kerne aus der Gleichgewichtskonfiguration ab, der für viele zweiatomige Moleküle und für die symmetrischen Streckschwingungen vieler mehratomiger Moleküle und Ionen im elektronischen Grundzustand zutrifft. Die berechneten Werte für die Ableitung der Polarisierbarkeit stimmen meist gut mit den aus den experimentell bestimmten Ramanintensitäten erhaltenen Werten überein. Mit Hilfe des Deltafunktionspotentialmodells errechneten wir aus den experimentell bestimmten Ableitungen der Polarisierbarkeit Bindungsordnungen für verschiedene ionische Systeme und erörterten die Ergebnisse im Hinblick auf die Beiträge der π- und σ-Elektronen zu den Ableitungen der Polarisierbarkeit von Mehrfachbindungen.

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  1. Department of Physics and Astronomy, Valdosta State College, Valdosta, Georgia, USA

    G. Nagarajan

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Nagarajan, G. Quantenmechanische Untersuchung absoluter Ramanintensitäten. Monatshefte für Chemie 103, 1232–1245 (1972). https://doi.org/10.1007/BF00904507

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