Analysis of [nu]2, [nu]4 Infrared Hot Bands of 32S16O3: Resolution of the Puzzle of the V1 CARS Spectrum

Published

November 1, 2002

Author(s)

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

Abstract

Further analysis of the high-resolution (0.0015 CM^-1) infrared spectrum of ³²S¹⁶0₃ has led to the assignment of more than 3100 hot band transitions from Ņ2 and Ņ4 levels to the states 2Ņ₂ (1=0), {nu]₂ + Ņ₄ (l= 1), and 2Ņ₄ (l=0, 2). These levels are strongly coupled via Fermi resonance and indirect Coriolis interactions to the Ņ₁ levels which are IR-inaccessible from the ground state. The unraveling of these interactions has allowed for the solution of the unusual and complicated structure of the Ņ₁ CARS spectrum. This has been accomplished by locating over 400 hot-band transitions to levels that contain at least 10% Ņ₁ character. The complex CARS spectrum results from a large number of energy level crossings between these states. Accurate rovibrational constants are deduced for all the mixed states for the first time, leading to deperturbed values of 1064.924 (11), 0,000 840 93(64), and 0.000 418 19 (58) CM ^-1 for Ņ_-1, α₁^{β, and α₁,}uc^ respectively. The uncertainties in the last digits are shown in parentheses and represent two standard deviations. In addition, new values for some of the anharmonicity constants have been obtained. Highly accurate values for the equilibrium rotational constants B_e and C_e are deduced, yielding independent, nearly identical values for the SO r_e bond length of 141.734.03(13)and 141.732 54(18) pm, respectively.

Citation

Journal of Molecular Spectroscopy

Volume

216

Issue

No. 1

Pub Type

Journals

Keywords

cars, high resolution, infrared, raman, sulfur troxide

Citation

Barber, J. , Chrysostom, E. , Masiello, T. , Nibler, J. , Maki, A. , Weber, A. , Blake, T. and Sams, R. (2002), Analysis of [nu]₂, [nu]₄ Infrared Hot Bands of ³²S¹⁶O₃: Resolution of the Puzzle of the V₁ CARS Spectrum, Journal of Molecular Spectroscopy (Accessed January 23, 2025)