FT-spectroscopy of the 12C18O rare isotopologue and deperturbation analysis of the A1Π(v = 3) level.

Research on 12C18O was carried out using two complementary Fourier-transform methods: (1) vacuum-ultraviolet absorption spectroscopy, with an accuracy ca. 0.03 cm-1 on the DESIRS beamline (SOLEIL synchrotron) and (2) visible emission spectroscopy with an accuracy of about 0.005-0.007 cm-1 by means of the Bruker IFS 125HR spectrometer (University of Rzeszów). The maximum rotational quantum number of the energy levels involved in the observed spectral lines was Jmax = 54. An effective Hamiltonian and the term-value fitting approach were implemented for the precise analysis of the A1Π(v = 3) level in 12C18O. It was performed by means of the PGOPHER code. The data set consisted of 571 spectral lines belonging to the A1Π-X1Σ+(3, 0), B1Σ+-A1Π(0, 3), C1Σ+-A1Π(0, 3) bands and several lines involving states that perturb the A1Π(v = 3) level as well as to the previously analysed B1Σ+-X1Σ+(0, 0) and C1Σ+-X1Σ+(0, 0) transitions. A significantly extended quantum-mechanical description of the A1Π(v = 3) level in 12C18O was provided. It consists of the 5 new unimolecular interactions of the spin-orbit and rotation-electronic nature, which had not been taken into account previously in the literature. The ro-vibronic term values of the A1Π(v = 3, Jmax = 55), a'3Σ+(v = 13), D1Δ(v = 4) and I1Σ-(v = 5) levels were determined with precision improved by a factor of 10 relative to the previously known values.