Abstract
Hydrogen cyanide (HCN) is a widely available molecule in planetary and
interplanetary environments. It has been observed that the
polymerization of HCN can lead to the formation of nucleobases and
proteins (Matthews & Minard 2006). Thus, HCN and its reactivity are
considered to be very important for prebiotic chemistry. Our evaluation
covers several molecules and oligomers, most of which have been
discussed in the literature (Ruiz-Bermejo et al., 2021), and ranks them
based on thermodynamic preference. In our study, we compute the relative
energies of a series of HCN-derived materials relative to HCN in liquid
water. We perform an automated search with semi-empirical methods to
extract the lowest energy conformers for each compound. Our work relies
on density functional theory (DFT) calculations with thermal corrections
coupled to an implicit solvation model to better emulate the
polymerization environments. These methodologies allow us to discuss the
impact of our results at relevant environments such as that of Saturn’s
Moon Titan or the early Earth conditions. The most stable HCN-derived
material in our set is the nucleobase adenine, computed to lie
~26 kcal mol-1 below HCN in a water solution. Our
enumeration of thermodynamically plausible reaction products and the
reaction routes for the abiotic formation of organic macromolecules
starting from simple units of HCN offers extensive insights into the
chemical and the physical limitations of suspected key prebiotic
processes (Sandström & Rahm 2021). 1. C. N. Matthews, R. D. Minard,
Faraday Discuss. 2006, 133, 393. 2. M. Ruiz-Bermejo, J. L. de la Fuente,
C. Pérez-Fernández, E. Mateo-Martí, Processes 2021, 9, 597. 3. H.
Sandström, M. Rahm, ACS Earth Space Chem. 2021, 5, 2152–2159.