title: Formamide reaction network in gas phase and solution via a unified theoretical approach: Toward a reconciliation of different prebiotic scenarios.
abstract: Increasing experimental and theoretical evidence points to formamide as a possible hub in the complex network of prebiotic chemical reactions leading from simple precursors like H2, H2O, N2, NH3, CO, and CO2 to key biological molecules like proteins, nucleic acids, and sugars. We present an in-depth computational study of the formation and decomposition reaction channels of formamide by means of ab initio molecular dynamics. To this aim we introduce a new theoretical method combining the metadynamics sampling scheme with a general purpose topological formulation of collective variables able to track a wide range of different reaction mechanisms. Our approach is flexible enough to discover multiple pathways and intermediates starting from minimal insight on the systems, and it allows passing in a seamless way from reactions in gas phase to reactions in liquid phase, with the solvent active role fully taken into account. We obtain crucial new insight into the interplay of the different formamide reaction channels and into environment effects on pathways and barriers. In particular, our results indicate a similar stability of formamide and hydrogen cyanide in solution as well as their relatively facile interconversion, thus reconciling experiments and theory and, possibly, two different and competing prebiotic scenarios. Moreover, although not explicitly sought, formic acid/ammonium formate is produced as an important formamide decomposition byproduct in solution.
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Université Pierre et Marie Curie, Sorbonne Universités, CNRS, Muséum National d'Histoire Naturelle, Institut de Recherche pour le Développement, UMR 7590, F-75005 Paris, France fabio.pietrucci@impmc.upmc.fr.
authors.forename: Fabio
authors.initials: F
authors.lastname: Pietrucci
authors.affiliation: Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Université Pierre et Marie Curie, Sorbonne Universités, CNRS, Muséum National d'Histoire Naturelle, Institut de Recherche pour le Développement, UMR 7590, F-75005 Paris, France.
authors.forename: Antonino Marco
authors.initials: AM
authors.lastname: Saitta
mesh_terms: D000641:Ammonia / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry; D005559:Formamides / Q000737:chemistry*; D005561:Formates / Q000737:chemistry; D056692:Prebiotics; D012996:Solutions
chemical_list: D005559:Formamides; D005561:Formates; D056692:Prebiotics; D012996:Solutions; C030544:formic acid; C031066:formamide; D000641:Ammonia; D002248:Carbon Monoxide
keywords: ab initio molecular dynamics; chemical reactions; formamide; free energy landscapes; prebiotic scenarios