On the potential catalytic role of electron capture in gas-phase condensation reactions: A theoretical exploratory study of the CH2O2 and CH3ON systems

The potential activation by electron capture of H-2 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, wh ose performances are compared in the evaluation of the negative electron af finities 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 o f 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 less than or equal to 2 eV for the incident electron.