The forbidden rotational Q branch of CH3SiF3: A study in internal rotation

The pure rotational spectrum driven by the small dipole moment produced perpendicular to the symmetry axis by centrifugal distortion has been investigated for CH₃SiF₃ in the ground vibrational state using a Fourier transform waveguide spectrometer. Between 10.9 and 17.0 GHz, four (k + 3 ← k) series in the Q branch have been measured in the lowest torsional state v₆ = 0 for k = 4, 5, 6, and 7 with 54 ? J ? 65. In each transition, the quantum number σ = 0, +1, −1 labelling the different torsional sub-levels is conserved. For given (J,k), splittings from ∼10 to ∼45 MHz have been observed between lines with different values of σ. The global data set includes the anticrossing molecular beam energy differences of W.L. Meerts, I. Ozier, Chem. Phys. 71 (1982) 401-415] as well as the mm-wave R branch frequencies and (A₁ − A₂) splittings of P. Dréan, J.-M. Colmont, J. Demaison, L. Dore, C. Degli Esposti, J. Mol. Spectrosc. 176 (1996) 23-27]). A good fit was obtained by varying 15 molecular parameters characterizing the torsion-rotation Hamiltonian H_TR for the vibrational ground state. Because of the strong correlation between two of the quartic torsion-distortion parameters (F_0,3K and D_0,Km) and a redundancy connecting the centrifugal distortion constants, four models were obtained yielding comparable fits. In each case, effective values were determined for the A-rotational constant and the height of the potential hindering the internal rotation. A high precision determination of the structural parameter ρ was made that is the same in all four models. For the off-diagonal quartic centrifugal distortion constant ε₀ and the sextic constants H_0,J, H_0,JK, H_0,KJ, and h_0,3, the differences in the values obtained in the two different reductions used have been explained in terms of the redundancy connecting these parameters. For σ = 0, +1, −1, the energy level pattern for (|k| = 3) is discussed for the case where the pure torsional energy splitting and the matrix elements off-diagonal in k are of comparable magnitude. A method is described of using an R branch study of the resulting σ-splittings for (|k| = 3) to probe the zeroth-order torsional Hamiltonian.