The B→X and D→X systems of XeF are recorded by photographing the emission from the low-pressure Xe*/XeF2 and Ar*/XeF2 reactions. A rotational analysis is obtained for the 1–2 band of B–X, for which isotopic blending is negligible. Vibrational parameters for the X, B, and D states are derived from a direct, weighted least-squares fit of all assignments for both transitions. Rotational parameters are deduced from the vibrational dependence of the band shapes and intensities. Some significant results of this analysis are ReX=2.293 å, ReB=2.631 å, ReD=2.51 Å, ωeX=225 cm−1, ωeB=309.0 cm−1, ωeD=350.1 cm−1, and 𝒟eX=1175 cm−1. The Franck–Condon factors for many of the bands in both systems show a strong rotational dependence, which is to be expected in transitions of this type, for reasons discussed herein.
B→X spontaneous and stimulated emission spectra of XeF have been photographed at medium resolution (2.0 Å/mm) and vibrationally analyzed. The assignments are made with the aid of trial-and-error Franck–Condon calculations and band profile simulations, which are described in detail. The strong laser emission near 3511 Å is primarily due to densely overlapped rotational lines in the 1–4 vibronic band, and that near 3532 Å probably includes numerous rotational transitions in the 0–2, 0–3, and 1–6 bands.
The B → X spectra of HgCl and HgI are studied at high resolution for the single isotopic species, 200Hg35Cl, 200Hg127I, and 200Hg129I. For HgI the analysis indicates that the v″ numbering should be decreased by one unit from the previous assignment. For both molecules the analyses deviate progressively from the previous assignments at high v″, extrapolating to lower estimates of the ground-state dissociation energies. Franck–Condon calculations yield ΔRe (=Re′ −Re″) =0.60Å for HgCl and 0.49 Å for HgI. The strongest laser features previously reported for HgCl occur near the heads of the overlapped 0–22, 1–23, 2–24, and 3–25 bands. The HgI laser operates in the region of the 0–14, 0–15, 1–15, 1–16, 2–17, and 2–18 bands.
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