On the Potential Catalytic Role of Electron Capture in Gas-Phase Condensation Reactions: A Theoretical Exploratory Study of the CH2O2 and CH3ON Systems

Abstract

The potential activation by electron capture of H2+CO2 or CO+H2O reactions, leading to HCOOH (formic acid), and of CO+NH3, HCN+H2O and HNC+H2O reactions, leading to HC(O)NH2 (formamide), have been studied theoretically. Ab initio calculations at the DFT, CCSD, CCSD(T) and QCISD(T) levels have been performed with the 6-311G(3df,2p) and 6-311+G(3df,2p) basis sets, whose performances are compared in the evaluation of the negative electron affinities of HCN and HNC. A routine method, CCSD/6-311+G(3df,2p)//B3LYP/6-311G(3df,2p), was then used for a survey of the potential energy surfaces of the above reactions. It has been shown that a promising reaction pathway was found in the catalytic anionic activation of HNC+H2O condensation, at an energy ≤2 eV for the incident electron.