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Analysis of the ν2, ν4 infrared hot bands and ν1 CARS spectrum of 34S16O3

✍ Scribed by Jeffrey Barber; Engelene t.H. Chrysostom; Tony Masiello; Joseph W. Nibler; Arthur Maki; Alfons Weber; Thomas A. Blake; Robert L. Sams

Book ID
104151787
Publisher
Elsevier Science
Year
2003
Tongue
English
Weight
227 KB
Volume
218
Category
Article
ISSN
0022-2852

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✦ Synopsis

High-resolution (0.0015 cm À1 ) infrared spectroscopy has been used to study the 34 S 16 O 3 IR-active hot bands originating from the m 2 and m 4 bending mode levels and terminating in the states 2m 2 ðl ¼ 0Þ, m 2 þ m 4 ðl ¼ AE1Þ, and 2m 4 ðl ¼ 0; AE2Þ. The upper states are strongly coupled via Fermi resonance and indirect Coriolis interactions to the m 1 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 m 1 for 34 S 16 O 3 is presented which is dramatically different from the corresponding one for 32 S 16 O 3 . From the infrared transitions, accurate rovibrational constants are deduced for all the mixed states, leading to deperturbed values for m 1 , a B 1 , and a C 1 of 1064.920(84), 0.000 834 5(54), and 0.000 410 (11) cm À1 , 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 ¼ 0:349 760 6(33) cm À1 and r e ¼ 141:734 70(68) pm, values that are identical (within experimental error) to those found for 32 S 16 O 3 .

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