On the Potential Catalytic Role of Electron Capture in Gas-Phase Condensation Reactions: A Theoretical Exploratory Study of the CH_2O_2 and CH_3ON Systems

摘要

The potential activation by electron capture of H_2 + CO_2 or CO + H_2O reactions, leading to HCOOH (formic acid), and of CO + NH_3, HCN + H_2O and HNC + H_2O reactions, leading to HC(O)NH_2 (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,wp), 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 + H_2O condensation, at an energy <= 2 eV for the incident electron.