Rate coefficients for rotational state-to-state transitions in H₂O + H₂O collisions for cometary and planetary applications, as predicted by mixed quantum-classical theory^★

Department of Chemistry, Marquette University, Milwaukee, WI 53233, USA
e-mail: dmitri.babikov@marquette.edu

Received: 14 December 2022
Accepted: 16 January 2023

Abstract

Aims. We present new calculations of collision cross sections for state-to-state transitions between the rotational states in an H₂O + H₂O system, which are used to generate a new database of collisional rate coefficients for cometary and planetary applications.

Methods. Calculations were carried out using a mixed quantum-classical theory approach that is implemented in the code MQCT. The large basis set of rotational states used in these calculations permits us to predict thermally averaged cross sections for 441 transitions in para- and ortho-H₂O in a broad range of temperatures.

Results. It is found that all state-to-state transitions in the H₂O + H₂O system split into two well-defined groups, one with higher cross-section values and lower energy transfer, which corresponds to the dipole-dipole driven processes. The other group has smaller cross sections and higher energy transfer, driven by higher-order interaction terms. We present a detailed analysis of the theoretical error bars, and we symmetrized the state-to-state transition matrixes to ensure that excitation and quenching processes for each transition satisfy the principle of microscopic reversibility. We also compare our results with other data available from the literature for H₂O + H₂O collisions.