The methane ν1(a1) vibrational state rotational structure obtained from high-resolution CARS-spectra of the Q-branch

The gaseous methane ν₁(a₁), Q-branch coherent anti-Stokes Raman scattering (CARS) spectra have been investigated at a resolution of 0.002 cm^?1. A complex rotational structure of the resolved Q-branch has been experimentally observed. This structure can be ascribed to strong tetrahedral splitting of the rotational levels of the upper vibrational state, which possibly occurs due to Fermi resonance between the ν₁(a₁) and 2ν₂(a₁) vibrational energy levels which are close to each other. An assignment of the observed spectral lines has been made, yielding the rotational constants B, D, and D_t for the ν₁(a₁) vibrational state of the methane molecule. The absolute Raman frequency ν₁ of the purely vibrational transition has been found.