On the formation of CN bonds in Titan's atmosphere-a unified reaction valley approach study

In this work, we investigated the formation of protonated hydrogen cyanide HCNH+ and methylene amine cation CH2NH2+ (both identified in Titan's upper atmosphere) from three different pathways which stem from the interaction between CH4 and N+ (P-3). As a mechanistic tool, we used the Unified Reaction Valley Approach (URVA) complemented with the Local Mode Analysis (LMA) assessing the strength of the CN bonds formed in these reactions. Our URVA studies could provide a comprehensive overview on bond formation/cleavage processes relevant to the specific mechanism of eight reactions R1-R8 that occur across the three pathways. In addition, we could explain the formation of CH2NH2+ and the appearance of HCNH+ and CHNH2+ along these paths. Although only smaller molecules are involved in these reactions including isomerization, hydrogen atom abstraction, and hydrogen molecule capture, we found a number of interesting features, such as roaming in reaction R-3 or the primary interaction of H-2 with the carbon atom in HCNH+ in reaction R8 followed by migration of one of the H-2 hydrogen atoms to the nitrogen which is more cost effective than breaking the HH bond first; a feature often found in catalysis. In all cases, charge transfer between carbon and nitrogen could be identified as a driving force for the CN bond formation. As revealed by LMA, the CN bonds formed in reactions R1-R8 cover a broad bond strength range from very weak to very strong, with the CN bond in protonated hydrogen cyanide HCNH+ identified as the strongest of all molecules investigated in this work. Our study demonstrates the large potential of both URVA and LMA to shed new light into these extraterrestrial reactions to help better understand prebiotic processes as well as develop guidelines for future investigations involving areas of complex interstellar chemistry. In particular, the formation of CN bonds as a precursor to the extraterrestrial formation of amino acids will be the focus of future investigations.