Quantum mechanical study of dehydration vs decarbonylation of formamide catalysed by amorphous silica surfaces
Formamide is abundant in the interstellar medium and was also present during the formation of the Solar system through the accretion process of the interstellar dust. Within the physico-chemical conditions of the primordial Earth it could have underwent decomposition, either via dehydration (HCN + H2O) or decarbonylation (CO + NH3). The first reactive channel provides HCN, which is an essential molecular building block for the formation of RNA/DNA bases, crucial for the emergence of life on Earth. In this work we studied, at CCSD(T)/pVTZ level, the two competitive routes of formamide decomposition, i.e. dehydration and decarbonylation, either in liquid formamide (by using the polarization continuum model tecnique), and at the interface between liquid formamide and amorphous silica. Amorphous silica was adopted as a convenient model of the crystalline silica phases, ubiquitous present in the primordial (and actual) Earth crust, and also due to its relevance in catalysis, adsorption and chromatography. Results show that: i) silica surface sites catalyse both decomposition channels by reducing the activation barriers of about 100 kJ mol-1 with respect to the reactions in homogeneous medium, and ii) the dehydration channel, giving rise to HCN, is strongly favoured from a kinetic standpoint over decarbonylation, the latter being, istead, slightly favoured from a thermodynamic point of view.