### Abstract

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 language | English |
---|---|

Article number | 044305 |

Pages (from-to) | 044305:1-5 |

Number of pages | 5 |

Journal | Journal of Chemical Physics |

Volume | 149 |

Issue number | 4 |

DOIs | |

Publication status | Published - 28 Jul 2018 |

### Scopus subject areas

- Physics and Astronomy(all)

### Cite this

*Journal of Chemical Physics*,

*149*(4), 044305:1-5. [044305]. https://doi.org/10.1063/1.5030977

}

*Journal of Chemical Physics*, vol. 149, no. 4, 044305, pp. 044305:1-5. https://doi.org/10.1063/1.5030977

**Non-Markovian rotational relaxation matrix for fast collisions between two linear molecules in high-pressure gaseous media. I. General formalism and preliminary testing.** / Kouzov, A.P.; Buldyreva, Jeanna V.; Sokolov, A.V.

Research output

TY - JOUR

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.

KW - столкновительная вращательная релаксация

UR - http://www.scopus.com/inward/record.url?scp=85050819963&partnerID=8YFLogxK

U2 - 10.1063/1.5030977

DO - 10.1063/1.5030977

M3 - Article

VL - 149

SP - 044305:1-5

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 4

M1 - 044305

ER -