PNNL

Abstract

The infrared spectrum of the v2, v4 bending mode region of 34S-substituted sulfur trioxide, 34S16O3, has been recorded at a resolution of 0.0025 cm-1. The v2 and v4 levels are coupled by a Coriolis interaction, yielding significant spectral shifts that have been successfully analyzed to obtain rovibrational constants for the ground state and both fundamentals. Comparisons are made with 32S16O3 parameters and the Bo rotational constant is found to be 0.348 556 04(28) cm-1, only very slightly larger than the corresponding value of 0.348 543 33(5) cm-1 for 32S16O3. Coriolis and l-type resonance interactions between the v2 and v4 levels produce frequency shifts and strong intensity perturbations in the spectra that are considered for both 34S16O3 and 32S16O3. The resulting analysis yields an average value of +0.62(8) for the dipole derivative ratio (?µx/?Q4x) (?µz/?Q2) and a positive sign for the product of this ratio with the ?y2,4 Coriolis constant, for which experiment gives +0.5940(15). Ab initio calculations indicate that the signs of ?µx/?Q4x and ?µz/?Q2 are both positive and hence ?y2,4 is also positive, in agreement with earlier calculations. These signs indicate that the effective charge movement in the xz plane has the same sense of rotation as Q2, Q4x atom motion in this plane that produces a py vibrational angular momentum component, correlated motion that is confirmed by ab initio calculations.