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Title: First analysis of the rotationally-resolved ν 2 and 2 ν 2 - ν 2 bands of sulfur dioxide, 33 S 16 O 2

Abstract

A Fourier transform spectrum of sulfur dioxide 33S16O2 has been recorded in the 18.3 µm spectral region at a resolution of 0.002 cm-1 using a Bruker IFS 125HR spectrometer leading to the observation of the ν2 and 2ν2- ν2 vibrational bands of the 33S16O2 molecule. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians. In this way it was possible to reproduce the upper state ro-vibrational levels to within the experimental uncertainty; i.e., ~0.20 x 10-3 cm-1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band centers: ν0 (ν2) =515.659089(50) cm-1, ν0 (2ν2) = 1030.697723(20) cm-1.

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1361952
Report Number(s):
PNNL-SA-120751
Journal ID: ISSN 0022-2852
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Molecular Spectroscopy; Journal Volume: 333
Country of Publication:
United States
Language:
English

Citation Formats

Blake, T. A., Flaud, J. -M., and Lafferty, W. J. First analysis of the rotationally-resolved ν 2 and 2 ν 2 - ν 2 bands of sulfur dioxide, 33 S 16 O 2. United States: N. p., 2017. Web. doi:10.1016/j.jms.2016.12.011.
Blake, T. A., Flaud, J. -M., & Lafferty, W. J. First analysis of the rotationally-resolved ν 2 and 2 ν 2 - ν 2 bands of sulfur dioxide, 33 S 16 O 2. United States. doi:10.1016/j.jms.2016.12.011.
Blake, T. A., Flaud, J. -M., and Lafferty, W. J. Wed . "First analysis of the rotationally-resolved ν 2 and 2 ν 2 - ν 2 bands of sulfur dioxide, 33 S 16 O 2". United States. doi:10.1016/j.jms.2016.12.011.
@article{osti_1361952,
title = {First analysis of the rotationally-resolved ν 2 and 2 ν 2 - ν 2 bands of sulfur dioxide, 33 S 16 O 2},
author = {Blake, T. A. and Flaud, J. -M. and Lafferty, W. J.},
abstractNote = {A Fourier transform spectrum of sulfur dioxide 33S16O2 has been recorded in the 18.3 µm spectral region at a resolution of 0.002 cm-1 using a Bruker IFS 125HR spectrometer leading to the observation of the ν2 and 2ν2- ν2 vibrational bands of the 33S16O2 molecule. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians. In this way it was possible to reproduce the upper state ro-vibrational levels to within the experimental uncertainty; i.e., ~0.20 x 10-3 cm-1. Very accurate rotational and centrifugal distortion constants were derived from the fit together with the following band centers: ν0 (ν2) =515.659089(50) cm-1, ν0 (2ν2) = 1030.697723(20) cm-1.},
doi = {10.1016/j.jms.2016.12.011},
journal = {Journal of Molecular Spectroscopy},
number = ,
volume = 333,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}
  • Cited by 2
  • A Fourier transform spectrum of sulfur dioxide 33S 16O 2 has been recorded in the 18.3 μm spectral region at a resolution of 0.002 cm $-$1 using a Bruker IFS 125HR spectrometer leading to the observation of the ν 2 and 2ν 22 vibrational bands of the 33S 16O 2 molecule. The corresponding upper state ro-vibrational levels were fit using Watson-type Hamiltonians. In this way it was possible to reproduce the upper state ro-vibrational levels to within the experimental uncertainty; i.e., ~ 0.20 × 10 $-$3 cm $-$1. Finally, very accurate rotational and centrifugal distortion constants were derived frommore » the fit together with the following band centers: ν 02) = 515.659089(50) cm $-$1, ν 0 (2ν 2) = 1030.697723(20) cm $-$1.« less
  • No abstract prepared.
  • The fifth of a series of publications on the high resolution rotation-vibration spectra of sulfur trioxide reports the results of a systematic study of the v3(é) and 2v3(A1'+E') infrared bands of the four symmetric top isotopomers 32S 16O 3, 34S 16O 3, 32S 18O 3, and 34S 18O 3. An internal coupling between the l = 0 and l = +2 levels of the 2v3 (A1'+E') states was observed. This small perturbation results in a level crossing between K-l = 9 and 12, in consequence of which the band origins of the A1', l=0 “ghost” states could be determined tomore » a high degree of accuracy. Ground and upper state rotational as well as vibrational anharmonicity constants are reported. The constants for the center-of-mass substituted species 32S 16O 3 and 34S 16O 3 vary only slightly, as do the constants for the 32S 18O 3, 34S 18O 3 pair. The S-O bond lengths for the vibrational ground states of the species 32S 16O 3, 34S 16O 3, 32S 18O 3 and 34S 18O 3, are, respectively, 141.981992(6), 141.979412(20), 150.605240(73), and 150.602348(73) pm, where the uncertainties, given in parentheses, are two standard deviations and refer to the last digits of the associated quantity.« less
  • We have obtained rotationally resolved pulsed field ionization photoelectron (PFI-PE) spectra for O[sub 2] in the energy range of 12.05[endash]18.15 eV, covering ionization transitions O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g], hthinsp;v[sup +]=0[endash]38,J[sup +])[l arrow]O[sub 2](X hthinsp;[sup 3][Sigma][sub g][sup [minus]], hthinsp;v[sup +]=0,N[sup [double prime]]). While the PFI-PE bands for O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g], v[sup +]=3[endash]5, 9, 11, 12, 22, and 25[endash]38) reported here are the first rotational-resolved photoelectron measurements, the PFI-PE bands for O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g], hthinsp;v[sup +]=25[endash]38) represent the first rotationally resolved spectroscopic data for these states. The simulation of spectra obtained at rotational temperaturesmore » of [approx]20 and 220 K allows the unambiguous identification of O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g], hthinsp;v[sup +][ge]21) PFI-PE bands, the majority of which overlap with prominent PFI-PE bands for O[sub 2][sup +](A hthinsp;[sup 2][Pi][sub u], hthinsp;v[sup +]=0[endash]12) and O[sub 2][sup +](a hthinsp;[sup 4][Pi][sub u], hthinsp;v[sup +]=0[endash]18). Combined with spectroscopic data obtained in the previous emission study and the present PFI-PE experiment, we have obtained accurate Dunham-type expansion coefficients for ionization energies, vibrational constants, rotational constants, and spin[endash]orbit splitting constants covering the O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g], hthinsp;v[sup +]=0[endash]38) states. Significant local intensity enhancements due to near-resonant autoionization were observed in PFI-PE bands for O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g], hthinsp;v[sup +]=0[endash]14). The energy region of these states is known to manifest a high density of very strong autoionizing low-[ital n]-Rydberg states. The observation of a long PFI-PE vibrational progression with a relatively smooth band intensity profile is also in accord with the direct excitation model for the production of highly vibrationally excited O[sub 2][sup +](X hthinsp;[sup 2][Pi][sub 1/2,3/2g]) states in the Franck[endash]Condon gap region. Since this experiment was carried out under relatively high rotational temperatures for O[sub 2], the PFI-PE data reveal higher rotational transitions and numerous local intensity enhancements, which were not observed in previous vacuum ultraviolet laser studies using a cold O[sub 2] molecular beam. The rotational branches found here indicate that photoelectrons are formed predominantly in continuum states with orbital angular momenta l=1,3, and 5. [copyright] [ital 1999 American Institute of Physics.]« less