High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands |
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Authors: | Ljiljana Puskar Evan G. Robertson Don McNaughton |
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Affiliation: | aSchool of Chemistry, Monash University, Wellington Road, Vic. 3800, Australia |
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Abstract: | We report a rovibrational analysis of the ν4 and ν6 fundamentals and the 2ν5 overtone of HNSO from high-resolution Fourier transform infrared spectra. The ν6 band (out-of-plane bend) centred at 757.5 cm−1 is c-type. The ν4 band (HNS bend) centred at 905.9 cm−1 is predominantly a-type with a very weak b-type component (). Numerous global perturbations and localized avoided crossings affecting the v4 = 1 rotational levels were successfully treated by inclusion of Fermi and c-axis Coriolis resonance terms between v4 = 1 and v5 = 2, and a b-axis Coriolis resonance term between v4 = 1 and v6 = 1. The latter term gives rise to an avoided crossing with an extraordinary ΔKa = 5 selection rule. The Fermi resonance between v4 = 1 and v5 = 2 gives rise to strong mixing of their rotational wavefunctions in the vicinity of Ka = 18. The resultant borrowing of intensity made it possible for 2ν5 transitions in the range Ka = 16–19 to be assigned and included in a global rovibrational treatment of all three band systems. |
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Keywords: | Thionylimide (HNSO) High-resolution IR spectroscopy Rovibrational analysis Spectral analysis by subtraction of simulated intensities (SASSI) |
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