Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments

Johnson, T. J.; Aker, P. M.; Scharko, N. K.; Williams, S. D.

doi:10.1016/j.jqsrt.2017.11.023

Title: Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments

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Abstract

Using vetted methods for generating quantitative absorption reference data, broadband infrared and near-infrared spectra (total range 11,000 – 600 cm-1) of pyridine vapor were recorded at 0.1 cm-1 spectral resolution, with the analyte thermostatted at 298 K and pressure-broadened to 1 atmosphere using N2 ballast gas. The quantitative spectrum is reported for the first time, and we have re-assigned some of the 27 fundamental modes. Fundamental assignments were confirmed by IR vapor phase band shapes, FT-Raman measurements and comparison with previous analyses. For the 760-Torr vapor-phase IR data several bands show resolved peaks (Q-branches). We have also assigned for the first time hundreds of combination and overtone bands in the mid- and near-IR. All assignments were made via comparison to theoretically calculated frequencies and intensities: The frequencies were computed with Gaussian03 with the anharmonic option, using MP2 and the ccpvtz basis set. The intensities were taken from a VSCF calculation in GAMESS using Hartree-Fock (for overtones and combination bands) or from the harmonic MP2 for fundamentals. Overtone and combination band harmonic and anharmonic frequencies, as well as intensities were also calculated using the CFOUR program. It is seen in the NIR spectrum near 6000 cm-1 that the very strong bandsmore »« less

Authors:: Johnson, T. J.; Aker, P. M.; Scharko, N. K.; Williams, S. D.

Publication Date:: Thu Feb 01 00:00:00 EST 2018

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1415691

Report Number(s):: PNNL-SA-128188
Journal ID: ISSN 0022-4073; 453040142

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Journal of Quantitative Spectroscopy and Radiative Transfer

Additional Journal Information:: Journal Volume: 206; Journal Issue: C; Journal ID: ISSN 0022-4073

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Citation Formats


                    Johnson, T. J., Aker, P. M., Scharko, N. K., and Williams, S. D. Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments.  United States: N. p., 2018. 
        Web.  doi:10.1016/j.jqsrt.2017.11.023.

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                    Johnson, T. J., Aker, P. M., Scharko, N. K., & Williams, S. D. Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments.  United States.  https://doi.org/10.1016/j.jqsrt.2017.11.023

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                    Johnson, T. J., Aker, P. M., Scharko, N. K., and Williams, S. D. 2018.  
        "Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments".  United States.  https://doi.org/10.1016/j.jqsrt.2017.11.023.

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@article{osti_1415691,

  title        = {Quantitative infrared and near-infrared gas-phase spectra for pyridine: Absolute intensities and vibrational assignments},

  author       = {Johnson, T. J. and Aker, P. M. and Scharko, N. K. and Williams, S. D.},

  abstractNote = {Using vetted methods for generating quantitative absorption reference data, broadband infrared and near-infrared spectra (total range 11,000 – 600 cm-1) of pyridine vapor were recorded at 0.1 cm-1 spectral resolution, with the analyte thermostatted at 298 K and pressure-broadened to 1 atmosphere using N2 ballast gas. The quantitative spectrum is reported for the first time, and we have re-assigned some of the 27 fundamental modes. Fundamental assignments were confirmed by IR vapor phase band shapes, FT-Raman measurements and comparison with previous analyses. For the 760-Torr vapor-phase IR data several bands show resolved peaks (Q-branches). We have also assigned for the first time hundreds of combination and overtone bands in the mid- and near-IR. All assignments were made via comparison to theoretically calculated frequencies and intensities: The frequencies were computed with Gaussian03 with the anharmonic option, using MP2 and the ccpvtz basis set. The intensities were taken from a VSCF calculation in GAMESS using Hartree-Fock (for overtones and combination bands) or from the harmonic MP2 for fundamentals. Overtone and combination band harmonic and anharmonic frequencies, as well as intensities were also calculated using the CFOUR program. It is seen in the NIR spectrum near 6000 cm-1 that the very strong bands arise from the C-H first overtones, whereas only much weaker bands are observed for combination bands of C-H stretching modes. Certain features are discussed for their potential utility for atmospheric monitoring.},

  doi          = {10.1016/j.jqsrt.2017.11.023},

  url          = {https://www.osti.gov/biblio/1415691},
  journal      = {Journal of Quantitative Spectroscopy and Radiative Transfer},

  issn         = {0022-4073},

  number       = C,

  volume       = 206,

  place        = {United States},

  year         = {Thu Feb 01 00:00:00 EST 2018},

  month        = {Thu Feb 01 00:00:00 EST 2018}

}

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