## 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.

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.

Translated title of the contribution | Немарковская релаксационная матрица для быстрых столкновений между двумя линейными молекулами в плотных газах. 1.Общий формализм и предварительное тестирование |
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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)