High resolution spectroscopy of asymmetric top molecules in nonsinglet electronic states: the ν3 fundamental of chlorine dioxide (16O35Cl16O) free radical in the X2B1 electronic ground state

Abstract

Highly resolved spectra of the ¹⁶O³⁵Cl¹⁶O isotopologue of chlorine dioxide were recorded with a Bruker IFS 125HR Fourier transform infrared spectrometer in the region of the ν₃ band. The analysis was made in the frame of the spin-rotational effective Hamiltonian (in A-reduction and I^r-representation) taking into account spin-rotational coupling operators up to the sixth order and the corresponding reduction of the Hamiltonian. The mathematical description of the ro-vibrational spectra was implemented to the specially created computer program ROVDES. Under the present experimental conditions, we were able to assign more than 5200 spin-rotational transitions to the ν₃ band. This number is 2.4 times higher compared to the previous studies available from the literature. The vibrational ground state parameters were improved, and the 2220 upper spin-rotation–vibration energy levels were determined and used as initial data in the inverse spectroscopic problem with the derived effective spin-rotational Hamiltonian. A total of 37 fitted parameters were determined (22 rotational and centrifugal parameters and 15 parameters of spin-rotation coupling). The appearance of strong Coriolis resonance interactions between the (001) and (100) vibrational states in the sets of (001)[N,K_a = 9], (001)[N,K_a = 17], (001)[N,K_a = 18] and (001)[N,K_a = 19] spin-rotation–vibration levels was experimentally observed for the first time and explained. The d_rms = 1.4 × 10⁻⁴ cm⁻¹ reproduction of the initial “experimental” upper ro-vibrational energy values was achieved which is considerably better compared to the use of parameters from a previous study ([J. Ortigoso et al., J. Mol. Spectrosc., 1992, 155, 25–43]).