High-resolution analysis of the 12.6 µm spectral region of the nitryl chloride (cas 13444-90-1) ClNO2 molecule

Add time:08/03/2019    Source:sciencedirect.com

The 12.6 µm region of nitryl chloride (cas 13444-90-1) (ClNO2) has been recorded at high resolution (0.00102 cm−1) using a Fourier transform spectrometer and the SOLEIL synchrotron light source. ClNO2 was found during our studies of chlorine nitrate and, after fractional distillations it was introduced into a multipass White cell made of inert materials, with an optical path length of 5.4 m. 320 scans were recorded for the range 600–980 cm−1 at a total pressure of 0.23 hPa and a temperature of 250 K. A thorough analysis of the ν2, 2ν6 and 2ν3 bands of 35ClNO2 and of the ν2 band of 37ClNO2 falling in this region has been carried out using a Hamiltonian model which takes explicitly into account the numerous resonances affecting the ro-vibrational energy levels; especially the C-type Coriolis resonance between the ν2 and the ν3 + ν6 modes. These two modes are only separated by less than 20 cm−1 and are thoroughly mixed. From the fittings, the following band centers were derived: νo(ν2) = 792.761264(60) cm−1, νo(ν3 + ν6) = 775.8923(20) cm−1, νo(2ν3) = 734.183576(20) cm−1 and νo(2ν6) = 819.836727(90) cm−1 for 35ClNO2 and νo(ν2) = 792.258284(30) cm−1 and νo(ν3 + ν6) = 774.6826(30) cm−1 for 37ClNO2 where the uncertainties are one standard deviation. Due to their sharp Q branches falling into an atmospheric “window”, the detection of the ν2 bands might be an advantageous route for future attempts to quantify atmospheric ClNO2, using infrared techniques.

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