Analysis of the Ņ2, Ņ4 Infrared Hot Bands and Ņ1 CARS Spectrum of 34S16O3

Published

February 1, 2003

Author(s)

J Barber, E T. Chrysostom, Tony Masiello, J Nibler, A G. Maki, A Weber, Thomas A. Blake, R L. Sams

Abstract

High-resolution (0.0015 cm^-1) infrared spectroscopy has been used to study the ³⁴S¹⁶O₃ IR-active hot bands originating from the Ņ₂ and Ņ₄ bending mode levels and terminating in the states 2Ņ₂ (I = 0), Ņ₂ + Ņ₄ (I = 1), and 2Ņ₄ (I = 0, 2). The upper states are strongly coupled via Fermi resonance and indirect Coriolis interactions to the Ņ₁ symmetric stretching mode levels that are only directly accessible from the ground state via a Raman-active transition. A Coherent anti-Stokes Raman (CARS) spectrum of Ņ₁ 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 Ņ₁, χ₁^B, and χ₁^C 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 B_e = 0.349 760 6(33) cm^-1 and r_e = 141.734 70(68) pm, values that are identical (within experimental error) to those found for ³²S¹⁶O₃.

Citation

Journal of Molecular Spectroscopy

Volume

218

Issue

No. 2

Pub Type

Journals

Keywords

CARS, coherent Raman, infrared, spectrum, sulfur trioxide, sulfur-34

Citation

Barber, J. , Chrysostom, E. , Masiello, T. , Nibler, J. , Maki, A. , Weber, A. , Blake, T. and Sams, R. (2003), Analysis of the Ņ₂, Ņ₄ Infrared Hot Bands and Ņ₁ CARS Spectrum of ³⁴S¹⁶O₃, Journal of Molecular Spectroscopy (Accessed October 31, 2024)