Semiempirical analysis of perturbations in the triplet 3s, 3d complex of the hydrogen molecule terms. Relative probabilities of the i3Πg -, j3Δg -→c3Πu + transitions in H2, HD, and D2

S. A. Astashkevich, B. P. Lavrov

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2 Scopus citations

Abstract

A semiempirical analysis is performed of data on electronic vibration-rotation (EVR) levels of mutually perturbed i3Π- and j3Δ- states and relative spontaneous emission probabilities for transitions from these states to the c3Πu state in H2 g and D2 molecules. The expansion coefficients for the perturbed wave functions in the Born-Oppenheimer basis for the H2, HD, and D2 molecules are obtained. Analysis of the isotope effect in the line strength ratios for various branches of the i3Πg -→c3Πu and j3Δg→c3Πu transitions showed that: (1) experimental data (76 values) are adequately described in the framework of the proposed nonadiabatic model with the help of a single variable parameter, namely, the ratio of the electronic dipole moments for these transitions, Mjc/Mic = -1.35±0.05; (2) the dependence of the above parameter on the internuclear distance r can be neglected in the range r = 1.5-3.0 a.u.; (3) the electron-rotation coupling of the b3Σu + and c3Πu + states is not essential at 10% accuracy of the relative line strength measurements. The obtained Mjc/Mic value agrees well with that determined by laser photofragmentation spectroscopy and differs by 20-30% from the ab initio value.

Original languageEnglish
Pages (from-to)38-47
Number of pages10
JournalOptics and Spectroscopy (English translation of Optika i Spektroskopiya)
Volume76
Issue number1
StatePublished - 1 Jan 1994

Scopus subject areas

  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

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