Research output: Contribution to journal › Article › peer-review
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. / Astashkevich, S. A.; Lavrov, B. P.
In: Optics and Spectroscopy (English translation of Optika i Spektroskopiya), Vol. 76, No. 1, 01.01.1994, p. 38-47.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - 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
AU - Astashkevich, S. A.
AU - Lavrov, B. P.
PY - 1994/1/1
Y1 - 1994/1/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0028257047&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0028257047
VL - 76
SP - 38
EP - 47
JO - OPTICS AND SPECTROSCOPY
JF - OPTICS AND SPECTROSCOPY
SN - 0030-400X
IS - 1
ER -
ID: 33270077