Effect of Localized Lattice Vibration on the Matrix Spectra of Diatomic Molecules

The effect of the interaction between the localized lattice vibrations and the rotational motion of a diatomic molecule trapped in rare-gas matrices on their matrix spectra is investigated theoretically. This results from the dependence of the crystalline field on the intermolecular separation. The...

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Bibliographic Details
Published in:The Journal of chemical physics 1968-01, Vol.49 (4), p.1555-1561
Main Author: Pandey, Gopal Krishna
Format: Article
Language:English
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Summary:The effect of the interaction between the localized lattice vibrations and the rotational motion of a diatomic molecule trapped in rare-gas matrices on their matrix spectra is investigated theoretically. This results from the dependence of the crystalline field on the intermolecular separation. The instantaneous interaction between the molecule–rare-gas atom is expanded in powers of the displacements of the lattice points from their equilibrium positions, and then this is averaged over all the neighboring atoms. The resulting self-energy of the molecule is then treated as a perturbation to calculate the displacement of the rotational levels. Expressions for the resulting shifts in the frequencies of the rotational transitions are given and this has been calculated in some typical cases to demonstrate the importance of this coupling between the localized lattice vibrations and the rotational motion of the molecule in the matrix.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1670278