Quantum Chemistry Study On The Reaction Of CH2NOH With NOx(X=1,2),OH

Oxime is an important substance in life and chemistry. Formaldehyde oxime (CH2NOH), which is the simplest oxime, was found in the atmosphere in recent years and the typical C = N double bond is the main structure. The thermal decomposition and photolysis processes of Formaldehyde oxime were studied by Paul J. etc. The main decomposition product, CH2NO, is an important chemical raw material, which can be used as propellant explosive agent. Furthermore, Formaldehyde oxime could react with the small molecules, such as OH, NO, NO2, the results could provide the theoretical evidence and possible way to restrain NOx pollutions. Therefore, it is important to study the nature and reactivity of the formaldehyde oxime molecules in the atmosphere.The main part of thesis begins with the theoretical studies on the reaction of CH2NOH with OH, NO, NO2. The mechanism and kinetic of these reaction have been investigated deeply. Furthermore, the method of topological analysis of electron density is applied to the studies on reaction pathways, which will be conducive to the reaction mechanisms of the transient species. The thesis consists of five chapters.In Chapter I, the studies on the formaldehyde oxime in recent years are introduced.In Chapter II, the quantum chemistry theory, the topological analysis of electron density and the relevant dynamics theory are summarized.In Chapter III, the reaction mechanism of CH2NOH with OH has been studied. Three reaction channels were found and CH2NO and H2O are the main products. The rate constants at different temperature of three reaction channel are determined. The topological structures changed are also discussed.In Chapter IV, the reaction mechanism of CH2NOH with NO has been studied. Among the five reaction channels, the reaction channels which generate CH2NO + HNO and ONHCHNOH are the main reaction channel, the former is the main reaction channel on the dynamics. The topological analyze of electron density were used to analyze the reaction mechanism.In Chapter V, the reaction mechanism of CH2NOH with NO2 has been studied. Thermodynamic and kinetic studies show that the response which generated CH2NO and HONO channel are the main reaction channels; the chemical bonding changes in chemical reactions and the topological properties at the critical points are analyzed.The innovations of this work include:1. For the first time, the reaction mechanism of CH2NOH with OH radicals, NO, NO2 molecules were studied by of thermodynamics and dynamics methods. The main reaction channels were found. The results provide the theoretical evidence for the existence of CH2NO, HCNOH, CH2NHO, HCN and HNO etc.2. The chemical bond changes were discussed by using the electron density topological analysis, the five-member ring structure is found in the reactions of CH2NOH with OH, NO.3. The systematic study on the reaction of CH2NOH with small molecules shows that for the species contains the C = N bond are relatively stable, the H atom which links to the C atom or the OH links to N atom are easily to reaction. These results can provide theoretical guidance for similar organic compounds.