Theoretical Treatment of the Coriolis Effect Using Hyperspherical Coordinates, with Application to the Ro-Vibrational Spectrum of Ozone.

Several alternative methods for the description of the interaction between rotation and vibration are compared and contrasted using hyperspherical coordinates for a triatomic molecule. These methods differ by the choice of the -axis and by the assumption of a prolate or oblate rotor shape of the molecule. For each case, a block-structure of the rotational-vibrational Hamiltonian matrix is derived and analyzed, and the advantages and disadvantages of each method are made explicit. This theory is then employed to compute ro-vibrational spectra of singly substituted ozone; roughly, 600 vibrational states of OOO and OOO isomers combined, with rotational excitations up to = 5 and both inversion parities (21600 coupled ro-vibrational states in total). Splittings between the states of different parities, so-called -doublings, are calculated and analyzed. The roles of the asymmetric-top rotor term and the Coriolis coupling term are determined individually, and it is found that they both affect these splittings, but in the opposite directions. Thus, the two effects partially cancel out, and the residual splittings are relatively small. Energies of the ro-vibrational states reported in this work for OOO and OOO are in excellent agreement with literature (available for low-vibrational excitation). New data obtained here for the highly excited vibrational states enable the first systematic study of the Coriolis effect in symmetric and asymmetric isotopomers of ozone.