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

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Abstract

In this work, we investigated the formation of protonated hydrogen cyanide HCNH+ and methylene amine cation CH\(_{2}\textit {NH}_{2}^{+}\) (both identified in Titan’s upper atmosphere) from three different pathways which stem from the interaction between CH4 and N+(3P). 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 CH\(_{2}\textit {NH}_{2}{\!}^{+}\) and the appearance of HCNH+ and CHNH\(_{2}{\!}^{+}\) 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 R3 or the primary interaction of H2 with the carbon atom in HCNH+ in reaction R8 followed by migration of one of the H2 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.

Formation of CN bonds in Titan’s atmosphere visualized via the reaction path curvature

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Acknowledgements

We thank SMU for generous computational resources.

Funding

This work was financially supported by the National Science Foundation, Grant 2102461.

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Authors and Affiliations

  1. Chemistry Department, SMU, Fondren Science Building, Dallas, 75275-0314, TX, USA

    Marek Freindorf, Nassim Beiranvand, Alexis A. A. Delgado, Yunwen Tao & Elfi Kraka

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  1. Marek Freindorf
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  2. Nassim Beiranvand
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  3. Alexis A. A. Delgado
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  4. Yunwen Tao
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  5. Elfi Kraka
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Corresponding author

Correspondence to Elfi Kraka.

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The authors declare no competing interests.

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Author contribution

Conceptualization, E.K.; methodology, E.K. and M.F.; pURVA coding and testing, YT; validation, M.F. and N.B.; formal analysis, N.B. and M.F.; investigation, N.B, M.F. and A.D.; data curation, N.B. and M.F.; writing (original draft preparation), E.K.; writing (review and editing), E.K., AD, and M.F. visualization, N.B. and M.F.; supervision, E.K.; project administration, E.K.; funding acquisition, E.K. All the authors have read and agreed to the published version of the manuscript.

Availability of data and materials

All data generated or analyzed during this study are included in this published article. Additional information is provided in the Supporting Information which contains (i) the decomposition of the reaction path direction along the reaction parameter s for each reaction; (ii) reaction movies following the changes of the reaction complex along the reaction parameter s for each reaction; (iii) Cartesian coordinates of molecules 1, 3–7, transition states TS1–TS6 and TS8, and some reference molecules.

Code availability

The local mode analysis package LModeA can be obtained by the authors upon request.

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Marek Freindorf and Nassim Beiranvand contributed equally to this work.

This article belongs to the Topical Collection: VIII Symposium on Electronic Structure and Molecular Dynamics – VIII SeedMol

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Freindorf, M., Beiranvand, N., Delgado, A.A.A. et al. On the formation of CN bonds in Titan’s atmosphere—a unified reaction valley approach study. J Mol Model 27, 320 (2021). https://doi.org/10.1007/s00894-021-04917-8

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