Abstract
Nineteen potential constants f in the internal-coordinate system up to the fourth-order for the OCS molecule were determined by a least-squares analysis. The observed vibrational frequencies v and the rotational constants Bv of six isotopic molecules (16O12C32S, 16O12C34S, 16O13C32S, 18O12C32S, 16O14C32S and 16O12C36S), 135 in total, were used as the observables in the calculation. The analysis was based on the second-order perturbation theory except that the Fermi resonances between v1 and 2v2 and between v3 and 2v2 were dealt with by solving a secular equation. The perturbation in the (20°1) state of 16O12C32S observed by Triaille and Courtoy was indispensable in the vibrational and rotational analysis. This perturbation was shown to be a third-order anharmonic resonance coupled with the (24°0) state, which was estimated to lie about 4 cm−1 below the (20°1) state, by the interaction term |W12| = 1.8 cm−1. The observed values of v and Bv for many other states were corrected for this type (ω3 ≈ 4ω2) of resonance, and were used in the least-squares analysis.
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