The A5Π–X5Π electronic transition of CrO, near 6000 Å, has been analysed in detail using laser-induced fluorescence and conventional discharge emission spectroscopy. The transition provides the first instance where it has been possible to analyse the rotational structures of quintet electronic states completely. Although the parallel polarization of the transition has prevented the spin–orbit coupling and Λ-doubling intervals from being observed directly, it is shown that sufficient indirect information exists in the spectrum for them to be obtained with fair precision. The excited state, A5Π, is perturbed by large numbers of other electronic states which have no intensity of their own for emission to the ground state. The analysis of the perturbed regions has been greatly facilitated by the laser-induced fluorescence spectra: the excitation spectra correspond to a rotational temperature close to room temperature (which offers a significant improvement in resolution over the discharge spectra), and the J-assignments of the perturbed lines given by the resolved fluorescence spectra are unambigious
If argon mixed with a small amount of NF3 is pumped rapidly through a mild discharge, a green glow is observed downstream from the discharge. This emission has been photographed with a high dispersion spectrograph and found to consist of a strong band with a head at 5 288 Å and a number of weaker bands. A rotational analysis of the bands has shown that they are the b1Σ+–X3Σ− bands of the NF molecule. The constants of the two states have been determined and it is found that for the ground state, ωe = 1 141.37 cm−1 and re = 1.317 3 Å.
The absolute rate constants for the reaction of H atoms with methyl- and vinyl-halides have been determined using esr spectroscopy and a conventional gas flow system. The rate constants determined at 298 ± 2 K at a pressure of 0.55 Torr are methane, (1.7 ± 0.3) × 10−17; ethane, (2.3 ± 0.5) × 10−17; methylfluoride, (4 ± 3) × 10−15; methylchloride, (8 ± 2) × 10−16; methylbromide, (2.1 ± 0.6) × 10−14; vinylfluoride, (1.47 ± 0.02) × 10−13; vinylchloride, (1.66 ± 0.08) × 10−13; and vinylbromide (4.07 ± 0.73) × 10−13 in units of cm3 molecule−1 s−1.
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