Trajectory-based simulation of far-infrared CIA profiles of CH$_4-$N$_2$ for modeling Titan's atmosphere

TL;DR

This paper presents a trajectory-based simulation method for far-infrared CIA profiles of CH₄-N₂ pairs, improving modeling of Titan's atmosphere spectra by combining high-level potential energy surfaces with classical trajectory analysis.

Contribution

It introduces a novel trajectory-based simulation approach using high-level PES and IDS data to accurately model CIA spectra of CH₄-N₂ relevant to Titan's atmosphere.

Findings

Simulated CIA profiles agree well with laboratory measurements.

A new semi-empirical model for CH₄-N₂ CIA is proposed.

Synthetic spectra match Cassini CIRS data across various angles.

Abstract

We report the results of the trajectory-based simulation of far-infrared collision-induced absorption (CIA) due to CH$_4-$N$_2$ pairs at temperatures between 70 and 400 K. Our analysis utilizes recently calculated high-level potential energy (PES) and induced dipole surfaces (IDS) [Finenko, A. A., Chistikov, D. N., Kalugina, Y. N., Conway E. K., Gordon, I. E., Phys. Chem. Chem. Phys., 2021, doi: 10.1039/d1cp02161c]. Treating collision partners as rigid rotors, the time evolution of interaction-induced dipole is accumulated over a vast ensemble of classical trajectories and subsequently transformed into CIA spectrum via Fourier transform. In our calculations, both bound and unbound states are properly accounted for, and the rigorous theory of lower-order spectral moments is addressed to check the accuracy of simulated profiles. Classically derived trajectory-based profiles are subject to two approximate desymmetrization procedures so that resulting profiles conform to the quantum principle of detailed balance. The simulated profiles are compared to laboratory measurements and employed for modeling Titan's spectra in the 50-500 cm$^{-1}$ range. Based on the desymmetrized simulated profiles, a new semi-empirical model for CH$_4-$N$_2$ CIA is proposed for modeling Titan's infrared spectra. Synthetic spectra derived using this model yield an excellent agreement with the data recorded by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft at low and high emission angles.