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The emission spectrum of HCN has been recorded at 1463 K using hot gas molecular emission (HOTGAME) spectroscopy in the wavenumber region of 2900–3500 cm1 with a resolution of 0.01 cm1. The dense emission spectrum was analyzed with the spectrum analysis software SyMath™ implemented in the Mathematica™ computer algebra system. This work reports the analysis of the 1vl 20 ! 0vl 20 band series up to v2 = 8 and of the 1vl 21 ! 0vl 21 band series up to v2 = 6.36 rovibronic (v1,v2, l,e/f,v3) substates of HCN including all l = 0,2,4,6,8 sublevels of the v1vl 2v3 ¼ 18l0 highly excited bending combination mode have been characterized for the first time and for the 22 known vibrational sublevels it was possible to improve the existing spectroscopic constants substantially. 18 (v1,v2, l,v3) vibrational sublevels are located for the first time relative to the 0000 state. The analysis reported here includes rovibrational states up to very large rotational excitations of J = 60–80. For the 1vl 20 combination states the rotational states have been determined up to J = 86 which corresponds to 7000 cm1 rotational excitation energy, this state is only 2000 cm1 below the isomerization barrier. It was possible to determine for the first time the Lv high order rotational constant for many states reported in this work
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