HCN production in Titan's Atmosphere: Coupling quantum chemistry and disequilibrium atmospheric modeling

TL;DR

This paper integrates quantum chemistry, experimental data, and atmospheric modeling to identify new reactions and accurately simulate hydrogen cyanide production in Titan's atmosphere, aligning well with observational data.

Contribution

It introduces a novel hybrid chemical network combining quantum chemistry and experimental data, revealing 33 new reactions and simplifying the modeling of HCN chemistry in Titan's atmosphere.

Findings

Discovered 33 new reactions with unknown rate coefficients.

Developed a reduced network of 19 reactions capturing most HCN production.

Simulated HCN profile matches Cassini observations.

Abstract

Hydrogen cyanide (HCN) is a critical reactive source of nitrogen for building key biomolecules relevant for the origin of life. Still, many HCN reactions remain uncharacterized by experiments and theory, and the complete picture of HCN production in planetary atmospheres is not fully understood. To improve this situation, we develop a novel technique making use of computational quantum chemistry, experimental data, and atmospheric numerical simulations. First, we use quantum chemistry simulations to explore the entire field of possible reactions for a list of primary species in N2-, CH4-, and H2-dominated atmospheres. In this process, we discover 33 new reactions with no previously known rate coefficients. From here, we develop a consistent reduced atmospheric hybrid chemical network (CRAHCN) containing experimental values when available, and our calculated rate coefficients otherwise. Next, we couple CRAHCN to a 1D chemical kinetic model (ChemKM) to compute the HCN abundance as a function of atmospheric depth on Titan. Our simulated atmospheric HCN profile agrees very well with the Cassini observations. CRAHCN contains 104 reactions however nearly all of the simulated atmospheric HCN profile can be obtained using a scaled down network of only 19 dominant reactions. From here, we form a complete picture of HCN chemistry in Titan's atmosphere, from the dissociation of the main atmospheric species, down to the direct production of HCN along 4 major channels. One of these channels was first discovered and characterized in Pearce et al. (2019) and this work.