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Title: The relaxation matrix for symmetric tops with inversion symmetry. I. Effects of line coupling on self-broadened ν1 and pure rotational bands of NH3

Abstract

Line mixing effects have been calculated in the ν1 parallel band of self-broadened NH3. The theoretical approach is an extension of a semi-classical model to symmetric-top molecules with inversion symmetry developed in the companion paper [Q. Ma and C. Boulet, J. Chem. Phys. 144, 224303 (2016)]. This model takes into account line coupling effects and hence enables the calculation of the entire relaxation matrix. A detailed analysis of the various coupling mechanisms is carried out for Q and R inversion doublets. The model has been applied to the calculation of the shape of the Q branch and of some R manifolds for which an obvious signature of line mixing effects has been experimentally demonstrated. Comparisons with measurements show that the present formalism leads to an accurate prediction of the available experimental line shapes. Discrepancies between the experimental and theoretical sets of first order mixing parameters are discussed as well as some extensions of both theory and experiment.

Authors:
 [1];  [2]
+ Show Author Affiliations
  1. Columbia Univ., New York, NY (United States)
  2. Univ. Paris-Saclay, Gif-sur-Yvette (France)
Publication Date:
Research Org.:
Columbia Univ., New York, NY (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE
OSTI Identifier:
1418594
Grant/Contract Number:  
AC02-05CH11231; NSF-1501297
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ma, Q., and Boulet, C. The relaxation matrix for symmetric tops with inversion symmetry. I. Effects of line coupling on self-broadened ν1 and pure rotational bands of NH3. United States: N. p., 2016. Web. doi:10.1063/1.4952995.
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Ma, Q., & Boulet, C. The relaxation matrix for symmetric tops with inversion symmetry. I. Effects of line coupling on self-broadened ν1 and pure rotational bands of NH3. United States. https://doi.org/10.1063/1.4952995
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Ma, Q., and Boulet, C. Tue . "The relaxation matrix for symmetric tops with inversion symmetry. I. Effects of line coupling on self-broadened ν1 and pure rotational bands of NH3". United States. https://doi.org/10.1063/1.4952995. https://www.osti.gov/servlets/purl/1418594.
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@article{osti_1418594,
title = {The relaxation matrix for symmetric tops with inversion symmetry. I. Effects of line coupling on self-broadened ν1 and pure rotational bands of NH3},
author = {Ma, Q. and Boulet, C.},
abstractNote = {Line mixing effects have been calculated in the ν1 parallel band of self-broadened NH3. The theoretical approach is an extension of a semi-classical model to symmetric-top molecules with inversion symmetry developed in the companion paper [Q. Ma and C. Boulet, J. Chem. Phys. 144, 224303 (2016)]. This model takes into account line coupling effects and hence enables the calculation of the entire relaxation matrix. A detailed analysis of the various coupling mechanisms is carried out for Q and R inversion doublets. The model has been applied to the calculation of the shape of the Q branch and of some R manifolds for which an obvious signature of line mixing effects has been experimentally demonstrated. Comparisons with measurements show that the present formalism leads to an accurate prediction of the available experimental line shapes. Discrepancies between the experimental and theoretical sets of first order mixing parameters are discussed as well as some extensions of both theory and experiment.},
doi = {10.1063/1.4952995},
journal = {Journal of Chemical Physics},
number = 22,
volume = 144,
place = {United States},
year = {Tue Jun 14 00:00:00 EDT 2016},
month = {Tue Jun 14 00:00:00 EDT 2016}
}
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Journal Article:
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https://doi.org/10.1063/1.4952995
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Cited by: 8 works
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Figures / Tables:

Fig. 1 Fig. 1: The Fourier transform of $\mathbb F$100100(k, rc) (in ps-2) at T = 296 K where k is dimensionless and rc is given in Å.
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text, January 2012

  • Ma, Qiancheng; Tipping, R. H.; Lavrentieva, Nina N.
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Effects on calculated half-widths and shifts from the line coupling for asymmetric-top molecules
text, January 2014

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text, January 2013

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    Works referencing / citing this record:

    The relaxation matrix for symmetric tops with inversion symmetry. II. Line mixing effects in the ν 1 band of NH 3
    journal, June 2016

    • Boulet, C.; Ma, Q.
    • The Journal of Chemical Physics, Vol. 144, Issue 22
    • DOI: 10.1063/1.4952996

    Relaxation matrix for symmetric tops with inversion symmetry: Line coupling and line mixing effects on NH 3 lines in the 𝝂 4 band
    journal, April 2017

    • Ma, Q.; Boulet, C.; Tipping, R. H.
    • The Journal of Chemical Physics, Vol. 146, Issue 13
    • DOI: 10.1063/1.4979492

    Line shape parameters of PH 3 transitions: Theoretical studies of self-broadened widths and line mixing effects
    journal, June 2020

    • Boulet, C.; Ma, Q.
    • The Journal of Chemical Physics, Vol. 152, Issue 21
    • DOI: 10.1063/5.0008535
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      Figures / Tables found in this record:

      Fig. 1 (p. 5)figure
      Fig. 2 (p. 5)figure
      Fig. 3 (p. 6)figure
      Fig. 4 (p. 7)figure
      Fig. 5 (p. 7)figure
      Fig. 6 (p. 7)figure
      Fig. 7 (p. 8)figure
      Fig. 8 (p. 8)figure
      Table I (p. 8)table
      Fig. 10 (p. 9)figure
      Fig. 11 (p. 9)figure
      Fig. 9 (p. 9)figure
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