Water spectra in the region 4200-6250 cm−1, extended analysis of v1 + v2, v2 + v3, and 3v2 bands and confirmation of highly excited states from flame spectra and from atmospheric long-path observations

Semen Nikolaevich Mikhaïlenko, Vl G. Tyuterev, V. I. Starikov, K. K. Albert, B. P. Winnewisser, M. Winnewisser, G. Mellau, C. Camy-Peyret, R. Lanquetin, J. M. Flaud, J. W. Brault

    Research output: Contribution to journalArticle

    44 Citations (Scopus)

    Abstract

    Water vapor infrared spectra have been recorded at room temperature in the range 4200-6250 cm−1 at resolutions (FWHM) between 0.0053 and 0.0080 cm−1. The use of a White-type multireflection cell made large pressure x pathlength products possible up to 31.27 mbar × 288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10−26 cm−1/molecule cm−2 at T = 296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H2 16O (bands v1 + v2, v2 + v3, and 3v2). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H2O data was 5 × 10−3 cm−1 for line positions and 7 × 10−3 cm−1 for energy levels up to Jmax = 20 and Ka(max) = 13. Particular attention was paid to water lines in the transparency window 4200-5000 cm−1, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H2 16O (v1, v3, 2v2, v1 + v2, v2 + v3, 3v2, 4v2-v2, 2v2 + v3-v2, v1 + 2v2-v2) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.

    Original languageEnglish
    Pages (from-to)91-121
    Number of pages31
    JournalJournal of Molecular Spectroscopy
    Volume213
    Issue number2
    DOIs
    Publication statusPublished - 1 Jan 2002

    Fingerprint

    Atmospheric spectra
    Water piping systems
    Excited states
    flames
    Molecular electronics
    Hamiltonians
    Potential energy surfaces
    Water
    Steam
    Full width at half maximum
    Transparency
    Electron energy levels
    water
    excitation
    Data reduction
    Signal to noise ratio
    molecular electronics
    data reduction
    Infrared radiation
    mountains

    Keywords

    • Centrifugal distortion
    • H O
    • HO
    • IR spectroscopy
    • Nonrigid molecules
    • Resonances
    • Rovibrational levels
    • Transparency window
    • Water

    ASJC Scopus subject areas

    • Atomic and Molecular Physics, and Optics
    • Spectroscopy
    • Physical and Theoretical Chemistry

    Cite this

    Water spectra in the region 4200-6250 cm−1, extended analysis of v1 + v2, v2 + v3, and 3v2 bands and confirmation of highly excited states from flame spectra and from atmospheric long-path observations. / Mikhaïlenko, Semen Nikolaevich; Tyuterev, Vl G.; Starikov, V. I.; Albert, K. K.; Winnewisser, B. P.; Winnewisser, M.; Mellau, G.; Camy-Peyret, C.; Lanquetin, R.; Flaud, J. M.; Brault, J. W.

    In: Journal of Molecular Spectroscopy, Vol. 213, No. 2, 01.01.2002, p. 91-121.

    Research output: Contribution to journalArticle

    Mikhaïlenko, Semen Nikolaevich ; Tyuterev, Vl G. ; Starikov, V. I. ; Albert, K. K. ; Winnewisser, B. P. ; Winnewisser, M. ; Mellau, G. ; Camy-Peyret, C. ; Lanquetin, R. ; Flaud, J. M. ; Brault, J. W. / Water spectra in the region 4200-6250 cm−1, extended analysis of v1 + v2, v2 + v3, and 3v2 bands and confirmation of highly excited states from flame spectra and from atmospheric long-path observations. In: Journal of Molecular Spectroscopy. 2002 ; Vol. 213, No. 2. pp. 91-121.
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    abstract = "Water vapor infrared spectra have been recorded at room temperature in the range 4200-6250 cm−1 at resolutions (FWHM) between 0.0053 and 0.0080 cm−1. The use of a White-type multireflection cell made large pressure x pathlength products possible up to 31.27 mbar × 288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10−26 cm−1/molecule cm−2 at T = 296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H2 16O (bands v1 + v2, v2 + v3, and 3v2). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H2O data was 5 × 10−3 cm−1 for line positions and 7 × 10−3 cm−1 for energy levels up to Jmax = 20 and Ka(max) = 13. Particular attention was paid to water lines in the transparency window 4200-5000 cm−1, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H2 16O (v1, v3, 2v2, v1 + v2, v2 + v3, 3v2, 4v2-v2, 2v2 + v3-v2, v1 + 2v2-v2) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.",
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    T1 - Water spectra in the region 4200-6250 cm−1, extended analysis of v1 + v2, v2 + v3, and 3v2 bands and confirmation of highly excited states from flame spectra and from atmospheric long-path observations

    AU - Mikhaïlenko, Semen Nikolaevich

    AU - Tyuterev, Vl G.

    AU - Starikov, V. I.

    AU - Albert, K. K.

    AU - Winnewisser, B. P.

    AU - Winnewisser, M.

    AU - Mellau, G.

    AU - Camy-Peyret, C.

    AU - Lanquetin, R.

    AU - Flaud, J. M.

    AU - Brault, J. W.

    PY - 2002/1/1

    Y1 - 2002/1/1

    N2 - Water vapor infrared spectra have been recorded at room temperature in the range 4200-6250 cm−1 at resolutions (FWHM) between 0.0053 and 0.0080 cm−1. The use of a White-type multireflection cell made large pressure x pathlength products possible up to 31.27 mbar × 288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10−26 cm−1/molecule cm−2 at T = 296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H2 16O (bands v1 + v2, v2 + v3, and 3v2). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H2O data was 5 × 10−3 cm−1 for line positions and 7 × 10−3 cm−1 for energy levels up to Jmax = 20 and Ka(max) = 13. Particular attention was paid to water lines in the transparency window 4200-5000 cm−1, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H2 16O (v1, v3, 2v2, v1 + v2, v2 + v3, 3v2, 4v2-v2, 2v2 + v3-v2, v1 + 2v2-v2) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.

    AB - Water vapor infrared spectra have been recorded at room temperature in the range 4200-6250 cm−1 at resolutions (FWHM) between 0.0053 and 0.0080 cm−1. The use of a White-type multireflection cell made large pressure x pathlength products possible up to 31.27 mbar × 288.5 m. The high signal-to-noise ratio allowed us to observe lines with intensities as small as 10−26 cm−1/molecule cm−2 at T = 296 K. Among about 5100 recorded water lines, about half of which are reported for the first time, 2351 lines have been assigned to the second triad of H2 16O (bands v1 + v2, v2 + v3, and 3v2). This has allowed the determination of line positions and corresponding upper rovibrational states with considerably improved accuracy. The assignments of certain highly excited states have been confirmed by the analysis of flame spectra and hot emission spectra. New values of effective Hamiltonian parameters for the upper states {(110), (030), (011)} have been determined. The generating function model was used in the data reduction to account for the anomalously strong centrifugal distortion of the rovibrational levels and resonance interactions. The RMS standard deviation of the least-squares fit of the assigned H2O data was 5 × 10−3 cm−1 for line positions and 7 × 10−3 cm−1 for energy levels up to Jmax = 20 and Ka(max) = 13. Particular attention was paid to water lines in the transparency window 4200-5000 cm−1, in which existing databases are not sufficient. In this region, 1395 lines of four isotopic species of water have been recorded and over 900 accurate line positions of nine bands of H2 16O (v1, v3, 2v2, v1 + v2, v2 + v3, 3v2, 4v2-v2, 2v2 + v3-v2, v1 + 2v2-v2) are reported in this range. A comparison of laboratory spectra with long path atmospheric spectra (20 km slant path in the mountains) in this region shows that many lines missing from available spectroscopic compilations (or considerably shifted compared to observations) are important for a proper interpretation of atmospheric observations. A comparison of the observed data with the best available predictions from the molecular electronic potential energy surface is discussed.

    KW - Centrifugal distortion

    KW - H O

    KW - HO

    KW - IR spectroscopy

    KW - Nonrigid molecules

    KW - Resonances

    KW - Rovibrational levels

    KW - Transparency window

    KW - Water

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    U2 - 10.1006/jmsp.2002.8558

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