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Title: Line shape parameters of PH 3 transitions in the Pentad near 4–5 μm: Self-broadened widths, shifts, line mixing and speed dependence

Abstract

Accurate knowledge of spectroscopic line parameters of PH 3 is important for remote sensing of the outer planets, especially Jupiter and Saturn. In a recent study, line positions and intensities for the Pentad bands of PH 3 have been reported from analysis of high-resolution, high signal-to noise room-temperature spectra recorded with two Fourier transform spectrometers (2014) [1]. The results presented in this study were obtained during the analysis of positions and intensities, but here we focus on the measurements of spectral line shapes (e.g. widths, shifts, line mixing) for the 2ν 4, ν 2 + ν 4, ν 1 and ν 3 bands. A multispectrum nonlinear least squares curve fitting technique employing a non-Voigt line shape to include line mixing and speed dependence of the Lorentz width was employed to fit the spectra simultaneously. The least squares fittings were performed on five room-temperature spectra recorded at various PH 3 pressures (~2–50 Torr) with the Bruker IFS-125HR Fourier transform spectrometer (FTS) located at the Pacific Northwest National Laboratory (PNNL), in Richland, Washington. Over 840 Lorentz self-broadened half-width coefficients, 620 self-shift coefficients and 185 speed dependence parameters were measured. Line mixing was detected for transitions in the 2ν 4, ν 1 andmore » ν 3 bands, and their values were quantified for 10 A+A- pairs of transitions via off-diagonal relaxation matrix element formalism. The dependences of the measured half-width coefficients on the J and K rotational quanta of the transitions are discussed. The self-width coefficients for the ν 1 and ν 3 bands from this study are compared to the self-width coefficients for transitions with the same rotational quanta (J, K) reported for the Dyad (ν 2 and ν 4) bands. The measurements from present study should be useful for the development of a reliable theoretical modeling of pressure-broadened widths, shifts and line mixing in symmetric top molecules with C 3v symmetry in general, and of PH 3 in particular.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1170472
Report Number(s):
PNNL-SA-105193
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Molecular Spectroscopy, 302:17-33
Country of Publication:
United States
Language:
English

Citation Formats

Malathy Devi, V., Benner, D. C., Kleiner, Isabelle, Sams, Robert L., and Fletcher, Leigh N.. Line shape parameters of PH3 transitions in the Pentad near 4–5 μm: Self-broadened widths, shifts, line mixing and speed dependence. United States: N. p., 2014. Web. doi:10.1016/j.jms.2014.06.003.
Malathy Devi, V., Benner, D. C., Kleiner, Isabelle, Sams, Robert L., & Fletcher, Leigh N.. Line shape parameters of PH3 transitions in the Pentad near 4–5 μm: Self-broadened widths, shifts, line mixing and speed dependence. United States. doi:10.1016/j.jms.2014.06.003.
Malathy Devi, V., Benner, D. C., Kleiner, Isabelle, Sams, Robert L., and Fletcher, Leigh N.. Fri . "Line shape parameters of PH3 transitions in the Pentad near 4–5 μm: Self-broadened widths, shifts, line mixing and speed dependence". United States. doi:10.1016/j.jms.2014.06.003.
@article{osti_1170472,
title = {Line shape parameters of PH3 transitions in the Pentad near 4–5 μm: Self-broadened widths, shifts, line mixing and speed dependence},
author = {Malathy Devi, V. and Benner, D. C. and Kleiner, Isabelle and Sams, Robert L. and Fletcher, Leigh N.},
abstractNote = {Accurate knowledge of spectroscopic line parameters of PH3 is important for remote sensing of the outer planets, especially Jupiter and Saturn. In a recent study, line positions and intensities for the Pentad bands of PH3 have been reported from analysis of high-resolution, high signal-to noise room-temperature spectra recorded with two Fourier transform spectrometers (2014) [1]. The results presented in this study were obtained during the analysis of positions and intensities, but here we focus on the measurements of spectral line shapes (e.g. widths, shifts, line mixing) for the 2ν4, ν2 + ν4, ν1 and ν3 bands. A multispectrum nonlinear least squares curve fitting technique employing a non-Voigt line shape to include line mixing and speed dependence of the Lorentz width was employed to fit the spectra simultaneously. The least squares fittings were performed on five room-temperature spectra recorded at various PH3 pressures (~2–50 Torr) with the Bruker IFS-125HR Fourier transform spectrometer (FTS) located at the Pacific Northwest National Laboratory (PNNL), in Richland, Washington. Over 840 Lorentz self-broadened half-width coefficients, 620 self-shift coefficients and 185 speed dependence parameters were measured. Line mixing was detected for transitions in the 2ν4, ν1 and ν3 bands, and their values were quantified for 10 A+A- pairs of transitions via off-diagonal relaxation matrix element formalism. The dependences of the measured half-width coefficients on the J and K rotational quanta of the transitions are discussed. The self-width coefficients for the ν1 and ν3 bands from this study are compared to the self-width coefficients for transitions with the same rotational quanta (J, K) reported for the Dyad (ν2 and ν4) bands. The measurements from present study should be useful for the development of a reliable theoretical modeling of pressure-broadened widths, shifts and line mixing in symmetric top molecules with C3v symmetry in general, and of PH3 in particular.},
doi = {10.1016/j.jms.2014.06.003},
journal = {Journal of Molecular Spectroscopy, 302:17-33},
number = ,
volume = ,
place = {United States},
year = {Fri Aug 01 00:00:00 EDT 2014},
month = {Fri Aug 01 00:00:00 EDT 2014}
}
  • A Bruker IFS-120HR Fourier transform spectrometer located at the Pacific Northwest National Laboratory (PNNL) in Richland, Washington was used to record a series of spectra of pure H 2O and air-broadened H 2O in the regions of the ν 1 and ν 3 bands (3450–4000 cm -1) at different pressures, temperatures and volume mixing ratios of H 2O in air. Eighteen high-resolution, high signal-to-noise (S/N) ratio absorption spectra were recorded at T = 268, 296 and 353 K using two temperature-controlled absorption cells with path lengths of 9.906(1) and 19.95(1) cm. Furthermore, the resolution of the spectra recorded with themore » 9.906 cm and 19.95 cm absorption cells was 0.006 and 0.008 cm -1, respectively. A multispectrum nonlinear least squares fitting technique was employed to fit all the eighteen spectra simultaneously to retrieve 313 accurate line positions, 315 intensities, 229 Lorentz air-broadened half-width and 213 air-shift coefficients and their temperature dependences (136 for air-broadened width and 128 for air-shift coefficients, respectively). Room temperature self-broadened half-width coefficients for 209 transitions and self-shift coefficients for 106 transitions were also measured. Line mixing coefficients were experimentally determined for isolated sets of 10 transition pairs for H 2O-air and 8 transition pairs for H 2O-H 2O using the off-diagonal relaxation matrix element formalism, and 85 quadratic speed dependence parameters were measured. Modified Complex Robert-Bonamy (MCRB) calculations of self-, and air-broadened (from N 2- and O 2-broadening) half-width and air-shift coefficients, and temperature dependence exponents of air-broadened half-width coefficients are made. Finally, the measurements and calculations are compared with each other and with similar parameters reported in the literature.« less
  • In order to improve the spectroscopic database for remote sensing of the giant planets, line positions and intensities are determined for the five bands (2ν 2, ν 2 + ν 4, 2ν 4, ν 1 and ν 3) that comprise the Pentad of PH 3 between 1950 and 2450 cm -1. Knowledge of PH 3 spectral line parameters in this region is important for the exploration of dynamics and chemistry on Saturn, (using existing Cassini/VIMS observations) and future near-IR data of Jupiter from Juno and ESA’s Jupiter Icy Moons Explorer (JUICE). For this study, spectra of pure PH 3 frommore » two Fourier transform spectrometers were obtained: (a) five high-resolution (0.00223 cm -1), high signal-to-noise (~1800) spectra recorded at room temperature (298.2 K) with the Bruker IFS 125HR Fourier transform spectrometer (FTS) at the Pacific Northwest National Laboratory (PNNL), Richland, Washington and (b) four high-resolution (at 0.0115 cm -1 resolution), high signal-to-noise (~700) spectra recorded at room temperature in the region 1800–5200 cm -1 using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory (NSO) on Kitt Peak. Individual line parameters above 2150 cm -1 were retrieved by simultaneous multispectrum fittings of all five Bruker spectra, while retrievals with the four Kitt Peak spectra were done in the 1938–2168 cm -1 range spectrum by spectrum and averaged. In all, positions and intensities were obtained for more than 4400 lines. These included 53 A+A- split pairs of transitions (arising due to vibration–rotation interactions (Coriolis-type interaction) between the ν 3 and ν 1 fundamental bands) for K" = 3, 6, and 9. Over 3400 positions and 1750 intensities of these lines were ultimately identified as relatively unblended and modeled up to J = 14 and K = 12 with rms values of 0.00133 cm -1 and 7.7%, respectively. The PH 3 line parameters (observed positions and measured intensities with known quantum assignments) and Hamiltonian constants are reported. Finally, comparisons with other recent studies are discussed.« less
  • The reduction of ReO{sub 4}{sup {minus}} with 2-hydrazinopyridine dihydrochloride and PPh{sub 3} gives [ReCl(PPh{sub 3}){sub 2}(NHNC{sub 5}H{sub 4}N)-(HNNC{sub 5}H{sub 4}N)]Cl{sub 2} (2). A similar reaction using 2-hydrazino-2-imidazoline and PPh{sub 3} in methanol hydrochloric acid allows the preparation of [ReCl{sub 3}(PPh{sub 3}){sub 2}(NNC{sub 3}H{sub 4}N{sub 2})] (3). The reaction of the Re(III) complex [ReCl{sub 3}(NNC{sub 5}H{sub 4}NH)(HNNC{sub 5}H{sub 4}N)] (1), with 2-(Ph{sub 2}P)C{sub 6}H{sub 4}SH in methanol yields [Re{l_brace}2-(Ph{sub 2}P)C{sub 6}H{sub 4}S{r_brace}-{l_brace}2-(Ph{sub 2}PO)C{sub 6}H{sub 4}S{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)] (4) and [Re{l_brace}2-(Ph{sub 2}P)C{sub 6}H{sub 4}S{r_brace}{sub 2}(NNC{sub 5}H{sub 4}N)] (5). The same precursor with 2-(Ph{sub 2}PO)-6-(Me{sub 3}Si)C{sub 6}H{sub 3}SH gives [ReCl{l_brace}2-(Ph{sub 2}PO)-6-(Me{submore » 3}Si)C{sub 6}H{sub 3}S{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)] (6) and with PhP(C{sub 6}H{sub 4}SH-2){sub 2} yields [Re{l_brace}PhP(C{sub 6}H{sub 4}S-2){sub 2}{r_brace}(NNC{sub 5}H{sub 4}N)(HNNC{sub 5}H{sub 4}N)] (7).« less
  • We present high-sensitivity and high-spectral-resolution line-shape and line-intensity measurements of self-broadened O{sub 2} b {sup 1}{Sigma}{sub g}{sup +}(v=1)(leftarrow)X {sup 3}{Sigma}{sub g}{sup -}(v=0) band transitions measured using the Pound-Drever-Hall-locked frequency-stabilized cavity ring-down spectroscopy technique. We give collisional broadening parameters and take into account the line-narrowing effects described by Dicke narrowing or the speed dependence of collisional broadening. We compare line intensities measured with relative uncertainties below 0.4% to data available in the HITRAN spectroscopic database.
  • New technetium(I) complexes of bidentate pseudoallyl ligands as triazenido, formamidinato, and acetamidinato have been synthesized and characterized. X-ray structure determinations of (Tc(PMe/sub 2/Ph)/sub 2/(CO)/sub 2/(p-CH/sub 3/C/sub 6/H/sub 4/N-N-NC/sub 6/H/sub 4/CH/sub 3/-p)) (1a) and (Tc(PMe/sub 2/Ph)/sub 2/(CO)/sub 2/(C/sub 6/H/sub 5/N-C(CH/sub 3/)-NC/sub 6/H/sub 5/)) (1c) show the technetium atom in a distorted octahedral coordination geometry with two axial PMe/sub 2/Ph and two cis-CO groups and the chelate ligands, which form a four-membered ring with the metal. Compound 1a crystallizes in space group Pbca of the orthorhombic system with a = 11.036 (2) A, b = 14.657 (4) A, c = 38.92 (1)more » A, and R = 0.045 for 3381 diffractometer data with I greater than or equal to 3sigma(I). Compound 1c crystallizes in the same space group, Pbca, with a = 8.954 (3) A, b = 16.727 (2) A, c = 41.435 (5) A, and R = 0.035 for 4108 diffractometer data with I greater than or equal to 3sigma(I). 31 references, 2 figures, 6 tables.« less