Infrared spectrum and theoretical calculations of a higher-energy isomer of the CO-SO2 complex
Yun Liu1, Zening Huang1, Cheng Chen1
1College of Physical Science and Technology, Central China Normal University, Wuhan 430079, China. duanchx@ccnu.edu.cn.
Abstract:
The rovibrational spectrum of the CO-SO2 complex is measured in the CO fundamental region by direct absorption in a supersonic slit jet expansion. Two new vibrational bands are assigned to CO-SO2, and the observed transitions are analyzed using the standard Watson S-reduced asymmetric-top Hamiltonian. The band origin is observed at 2150.95502(18) cm-1 for band I and 2148.24081(39) cm-1 for band II, which shows a blue shift from that of the CO monomer by about +7.684 cm-1 and +4.753 cm-1, respectively. Band I is an ordinary a/c hybrid vibrational band, while only a-type transitions with even-Ka levels are observed in band II. A restricted 2-dimensional intermolecular potential energy surface (2D-IPES) is constructed at the MP2/aug-cc-PVTZ level of theory. Full geometry optimizations and harmonic frequency calculations are performed for stationary points on the 2D-IPES. Band I is attributed to the most stable C-bonded isomer of CO-SO2. Band II is attributed to a higher-energy O-bonded isomer with a vibrationally averaged planar structure of C2v symmetry.
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