Non-Markovian rotational relaxation matrix for fast collisions between two linear molecules in high-pressure gaseous media. I. General formalism and preliminary testing

A.P. Kouzov, Jeanna V. Buldyreva, A.V. Sokolov

Research output

Abstract

Collisional mixing of (vib)rotational lines appearing in spectroscopic signatures of dense planetary
atmospheres and combustion environments is rigorously handled for the case of two linear colliders
in terms of incomplete (non-Markovian) collisions related to off-energy-shell scattering amplitudes.
Contrary to the standard impact-approximation approaches valid solely in band-centre regions, a
new uniform broadband spectrum description is developed on the basis of a frequency-dependent
rotational relaxation matrix which accurately accounts for the influence of the extra photon energy
with respect to the molecular transitions. This matrix is built using a symmetric Liouville-space
metric and obeys all known fundamental rules. Its direct calculation from refined potential-energy
surfaces and promising modeling methods for forthcoming practical computations are outlined. A
simple preliminary test for N2–N2 isotropic Raman line widths argues in favor of considerable effects
of the internal perturber’s structure on modeled spectral characteristics.
Original languageEnglish
Article number044305
Pages (from-to)044305:1-5
Number of pages5
JournalJournal of Chemical Physics
Volume149
Issue number4
DOIs
Publication statusPublished - 28 Jul 2018

Scopus subject areas

  • Physics and Astronomy(all)

Cite this

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abstract = "Collisional mixing of (vib)rotational lines appearing in spectroscopic signatures of dense planetaryatmospheres and combustion environments is rigorously handled for the case of two linear collidersin terms of incomplete (non-Markovian) collisions related to off-energy-shell scattering amplitudes.Contrary to the standard impact-approximation approaches valid solely in band-centre regions, anew uniform broadband spectrum description is developed on the basis of a frequency-dependentrotational relaxation matrix which accurately accounts for the influence of the extra photon energywith respect to the molecular transitions. This matrix is built using a symmetric Liouville-spacemetric and obeys all known fundamental rules. Its direct calculation from refined potential-energysurfaces and promising modeling methods for forthcoming practical computations are outlined. Asimple preliminary test for N2–N2 isotropic Raman line widths argues in favor of considerable effectsof the internal perturber’s structure on modeled spectral characteristics.",
keywords = "столкновительная вращательная релаксация",
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T1 - Non-Markovian rotational relaxation matrix for fast collisions between two linear molecules in high-pressure gaseous media. I. General formalism and preliminary testing

AU - Kouzov, A.P.

AU - Buldyreva, Jeanna V.

AU - Sokolov, A.V.

PY - 2018/7/28

Y1 - 2018/7/28

N2 - Collisional mixing of (vib)rotational lines appearing in spectroscopic signatures of dense planetaryatmospheres and combustion environments is rigorously handled for the case of two linear collidersin terms of incomplete (non-Markovian) collisions related to off-energy-shell scattering amplitudes.Contrary to the standard impact-approximation approaches valid solely in band-centre regions, anew uniform broadband spectrum description is developed on the basis of a frequency-dependentrotational relaxation matrix which accurately accounts for the influence of the extra photon energywith respect to the molecular transitions. This matrix is built using a symmetric Liouville-spacemetric and obeys all known fundamental rules. Its direct calculation from refined potential-energysurfaces and promising modeling methods for forthcoming practical computations are outlined. Asimple preliminary test for N2–N2 isotropic Raman line widths argues in favor of considerable effectsof the internal perturber’s structure on modeled spectral characteristics.

AB - Collisional mixing of (vib)rotational lines appearing in spectroscopic signatures of dense planetaryatmospheres and combustion environments is rigorously handled for the case of two linear collidersin terms of incomplete (non-Markovian) collisions related to off-energy-shell scattering amplitudes.Contrary to the standard impact-approximation approaches valid solely in band-centre regions, anew uniform broadband spectrum description is developed on the basis of a frequency-dependentrotational relaxation matrix which accurately accounts for the influence of the extra photon energywith respect to the molecular transitions. This matrix is built using a symmetric Liouville-spacemetric and obeys all known fundamental rules. Its direct calculation from refined potential-energysurfaces and promising modeling methods for forthcoming practical computations are outlined. Asimple preliminary test for N2–N2 isotropic Raman line widths argues in favor of considerable effectsof the internal perturber’s structure on modeled spectral characteristics.

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U2 - 10.1063/1.5030977

DO - 10.1063/1.5030977

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