PNNL

Abstract

As part of a series of investigations of isotopic forms of sulfur trioxide, high-resolution infrared and coherent anti-Stokes Raman spectroscopies were used to study the fundamental modes and several hot bands of 32S18O3. Hot bands originating from the v2 and v4 bending mode levels have been found to couple strongly to the IR-inactive v1 symmetric stretching mode through indirect Coriolis interactions and Fermi resonances. Coriolis coupling effects are particularly noticeable in 32S18O3 due to the close proximity of the v2 and v4 fundamental vibrations, whose deperturbed wavenumber values are 486.488 13(4) and 504.284 77(4) cm-1. The uncertainties in the last digits are shown in parentheses and are two standard deviations. From the infrared transitions, accurate rovibrational constants are deduced for all of the mixed states, leading to deperturbed values for v1, and of 1004.68(2), 0.000 713(2), and 0.000 348(2) cm-1, respectively. The Be value is found to be 0.310 820(2) cm-1, yielding an equilibrium bond length re of 141.7333(4) pm that is, within experimental error, identical to the value of 141.7339(3) pm reported previously for 34S18O3. With this work, precise and accurate spectroscopic constants have now been determined in a systematic and consistent manner for all the fundamental vibrational modes of the sulfur trioxide D3h isotopomeric forms 32S16O3, 34S16O3, 32S18O3, and 34S18O3.