Calculation of vibration-rotation line intensities of polyatomic molecules based on the formalism of irreducible tensorial sets

V. N. Saveliev, O. N. Ulenikov

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Abstract

Irreducible tensorial sets of the point-symmetry groups are used to determine the general formulae for calculating the matrix elements of the reduced dipole moment operator of a polyatomic molecule. These general expressions allow different types of intramolecular interactions and accidental resonances to be considered. Transitions from one type of molecule to another are accounted for by substitution of isoscalar factors and 9 Gamma symbols of the point-symmetry group in the formulae. As an illustration the general expressions obtained are used to analyse the dependences of matrix elements of the reduced dipole moment on the rotational quantum numbers for some vibrational absorption bands of molecules with D3h, C3v and T d symmetries. For allowed transitions contributions to the reduced dipole moment operator which are linear and quadratic in Jalphaare taken into account. for forbidden transitions the main contributions are taken into account. It is shown that the general formulae obtained describe the generalised Herman-Wallis effect (1955) for polyatomic molecules.

Original languageEnglish
Article number012
Pages (from-to)67-83
Number of pages17
JournalJournal of Physics B: Atomic and Molecular Physics
Volume20
Issue number1
DOIs
Publication statusPublished - 1987

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polyatomic molecules
dipole moments
formalism
vibration
symmetry
operators
forbidden transitions
matrices
quantum numbers
molecules
substitutes
absorption spectra
interactions

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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