Rhodium monofluoride has been observed and spectroscopically characterized. RhF molecules were produced under jet-cooled conditions in a laser vaporization molecular beam source by the reaction of a laser-vaporized rhodium plasma with SF(6) doped in helium, and studied with laser-induced fluorescence spectroscopy under both medium and high resolution. More than 25 bands have been observed in laser-induced fluorescence between 18,500 and 24,500 cm(-1) and five of these have been recorded at 200 MHz resolution. All bands of appreciable intensity have been rotationally analyzed. The ground electronic levels has Omega=2, which is attributed to an inverted (3)Pi state from the 2 delta(4)6 pi(3)12 sigma(1) electron configuration. The ground level rotational constants are B=0.272 45 cm(-1), D=1.035 x 10(-7) cm(-1). Very small ground level Lambda doublings are evident in the spectrum. Excited states having Omega=1, 2, and 3 have been identified. Dispersed fluorescence spectroscopy from 11 excited levels has been used to locate a large number of low-lying vibronic states within the energy range up to 8,000 cm(-1). A ground state vibrational interval of approximately 575 cm(-1) is suggested.

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A number of experiments have been performed in an effort to better understand the photoinitiated chain decomposition of ClN3. Discharge-flow methods were used to determine the rate of energy exchange between vibrationally excited N2 (a likely chain carrier) and ClN3. The rate constant for energy transfer from N2(v=1) to ClN3 was found to be (2.0 ± 1.0) × 10-13 cm3 s-1 at 300 K. This process is thought to excite the ν2 mode in ClN3 with the release of 281 cm-1 of excess energy. Experiments were also performed in which the decomposition of ClN3 was initiated by photolysis with a pulsed KrF laser at 249 nm, with subsequent observation of the time dependence of the densities of ClN3, electronically excited NCl(aΔ), and vibrationally excited ClN3(ν2). A kinetic model for the ClN3 decomposition was assembled based on reactions with NCl(a1Δ) and N2(ν).

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