The Investigation Of Reaction Mechanisms Of FC(O)O With NO By Using Quantum Chemistry Methods

The thesis is focus on fluoroformyloxyl radicals, which plays an important role in atmospheric chemistry. The reactions of FC(O)O with NO and the geomeries of FC(O)ONO isomers and related isomerization reaction mechanisms and the geomeries of FC(O)O isomers and related isomerization reaction mechanisms are studied by using quantum chemistry methods and electronic density topological analysis method. The changes of chemical bonds in the reactions are also discussed, which will be helpful for the experimental research of the atmospheric chemistry. The paper consists of three parts, the first part presents the reaction mechanisms of FC(O)O with NO, the second part shows the studies of the structures of FC(O)ONO isomers and isomerization reaction mechanisms of them, the third part shows the studies of the structures of FC(O)O and FC(O)H isomers and isomerization reaction mechanisms of them .In the first chapter, an all-around introduction to the previous experimental and theoretical studies on the reactions of fluoroformyloxyl radicals is presented.In the second chapter, the developments and applications of modern quantum chemistry theory and quantum topological theory are described briefly.In the third chapter, the reaction mechanisms of FC(O)O radical with NO are investigated. Four reaction channels have been found and the energy Barrier of FC(O)O + NO→COM2→TS3→FNO+CO₂ and FC(O)O + NO→COM2→TS4-1→COM3→TS4-2→FN(O)O+CO is not too high which means the reactions are very easy. The former is determined to be the main channel. Furthermore, the result shows that there are two kinds of transition structures in the reactions of FC(O)O radical with NO: T-shaped conflict-type structure and ring bifurcation-type structure. Furthermore, the energy transition state and structure transition state are found by topological analysis of electronic density in the discussion of microcosmic reaction mechanisms.In the fourth chapter, the structures of FC(O)ONO isomers and isomerization reaction mechanisms of them are studied. 12 isomers and 5 isomerization reaction mechanisms of FC(O)ONO are found. The reaction channels and the changes of chemical bonds in the reactions were discussed by using topological analysis of electronic density.In the fifth chapter, the structures of FC(O)O and FC(O)H isomers and isomerization reaction mechanisms of them are studied. The possible reaction channels were found for the reactions.The reaction channels and the changes of chemical bonds in the reactions were discussed by using topological analysis of electronic density.The novel conclusions and ideas of this work are listed as follows:1.Four reaction channels have been found and aggregated in the reaction of FC(O)O with NO and the energy Barrier of FC(O)O + NO→COM2→TS3→FNO+ CO₂ and FC(O)O + NO→COM2→TS4-1→COM3→TS4-2→FN(O)O+CO is not too high which means the reactions are very easy. The former is determined to be the main channel. Furthermore, the result shows that there are two kinds of transition structures in the reactions of FC(O)O radical with NO: T-shaped conflict-type structure and ring bifurcation-type structure. The energy transition state and structure transition state are found by topological analysis of electronic density in the discussion of microcosmic reaction mechanisms.2.The structures of FC(O)ONO isomers and isomerization reaction mechanisms of them are studied. 12 isomers and 5 isomerization reaction mechanisms of FC(O)ONO are found. 8 isomers and 4 isomerization reaction mechanisms are found for the first time.3.The structures of FC(O)O and FC(O)H isomers and isomerization reaction mechanisms of them are studied for the first time. The reaction channels and the changes of chemical bonds in the reactions were discussed by using topological analysis of electronic density.