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On the Potential Catalytic Role of Electron Capture in Gas‐Phase Condensation Reactions: A Theoretical Exploratory Study of the CH 2 O 2 and CH 3 ON Systems
Author(s) -
Chevreau Hilaire,
Gardebien Fabrice,
DézarnaudDandine Christine,
Sevin Alain
Publication year - 2001
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/1439-7641(20011015)2:10<583::aid-cphc583>3.0.co;2-7
Subject(s) - chemistry , formamide , catalysis , ab initio , ab initio quantum chemistry methods , formic acid , computational chemistry , molecule , organic chemistry
The potential activation by electron capture of H 2 +CO 2 or CO+H 2 O reactions, leading to HCOOH (formic acid), and of CO+NH 3 , HCN+H 2 O and HNC+H 2 O 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,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+H 2 O condensation, at an energy ≤2 eV for the incident electron.