High-resolution (0.0015 cm-1) infrared spectroscopy has been used to study the 34S16O3 IR-active hot bands originating from the v2 and v4 bending mode levels and terminating in the states 2v2 (l=0), v2+v4 (l=+1), and 2v4 (1=0, +2). The upper states are strongly coupled via Fermi resonance and indirect Coriolis interactions to the v1 symmetric stretching mode levels that are only directly accessible from the ground state via a Raman-active transition. A Coherent anit-Stokes Raman (CARS) spectrum of v1 for 34S16O3 is presented which is dramatically different from the corresponding one for 32S16O3. From the infrared transitions, accurate rovibrational constants are deduced for all the mixed states, leading to deperturbed values for v1, a1B, and a1C of 1064.920(84), 0.000 834 5 (54), and 0.000 410(11) cm-1 respectively. The uncertainties in the last digits are shown in parentheses and represent two standard deviations. These parameters reproduce the unresolved Q-branch contour of the CARS spectrum very well. Various other rotational and vibrational parameters have been determined, leading to values of Be = 0.349 760 6(33) cm-1 and re = 141.734 70(68) pm, values that are identical (within experimental error) to those found for 32S16O3.
Revised: March 31, 2004 |
Published: April 1, 2003
Citation
Barber J.B., E. Chrysostom, T. Masiello, J.W. Nibler, A. Maki, A. Weber, and T.A. Blake, et al. 2003.Analysis of the v2, v4 Infrared Hot Bands and v1 CARS Spectrum of 34S16O3.Journal of Molecular Spectroscopy 218, no. 2:204-212.PNNL-SA-38044.