The Atmospheric Important Species Fno_x Of (x = 1,2) Electronic Structure Of Performance And Related Reactions

In this thesis, FNO and FNO2 were studied using quantum chemistry method and the topological analysis of electronic density. Geometry, electronic structure, chemical bonds and relevant reaction mechanisms of these species were discussed. The results will provide useful information on the structure and reactive capacity of atmospheric species FNO and FNO2. The main studies consist of four parts, the first part presents the isomerization reaction mechanisms of FNO and FON, the second part shows the structures of (H)FNO+ isomers and isomerization reaction mechanisms of them, the third part shows the structures of FNO2 isomers and isomerization reaction mechanisms of them, and the last part gives the reaction mechanisms of FNO, FNO2 with O3.The studies on the isomerization reaction mechanism of FNO and FON were presented in the first part. The possible reaction channel was found for the reaction. According to Bader's theory of"AIM", the characteristics of the chemical bonds were described quantitatively according to the change of electronic density and the Laplacian. The structure transition state and the energy transition state were found in the isomerization reaction of FNO and FON, and the structure transition state was three-member ring structure.In the second part, eight possible isomers of (H)FNO+ in atmosphere were studied, and the charge density difference of molecule formation for (H)FNO+ isomers were made using GTA2000 program, the electron current was observed directly after FNO and FON protonated, the electron on H atom was increased, while the electron on F atom was reduced except in (H)FNO+. The isomerization mechanisms of (H)FNO+ can be divided into four kinds: molecular partial rotation, H migration, F migration and molecular relative vibration. Three typical reactions were analyzed using the topological analysis of electronic density. The process of HFNO+â†'FN(H)O+ and FNOH+-transâ†'FO(H)N+ experienced H migration and the F migration respevtively, the three-member ring structure transition state, then the energy transition state; The process of FNOH+-cisâ†'HFNO+ experienced H migration, the four-member ring structure transition, the energy transition state was in the ringed transition region.In the third part, the nine possible isomers of FNO2 in atmosphere were studied. The isomerization mechanisms of FNO2 can be divided into four kinds: molecular partial rotation, atom migration, molecular relative vibration, omnibus mechanisms that the molecular framework recombined with atom migration or with molecular partial rotation. Three typical reactions were analyzed using the topological analysis of electronic density. The process of FNOO-cisâ†'FO(O)N experienced the three-member ring structure transition state, then the energy transition state. The process of FNOO-cisâ†'FOON-cis experienced the four-member ring structure transition state, and the energy transition state was in the ringed transition region.The process of FONO-transâ†'FOON-cis experienced the three-member ring structure transition state first, then a non-planar four-member ring structure transition state, while the energy transition state was in the four-member ring transition region. The studies on the reaction mechanisms of FNO, FNO2 with O3 were presented in the last part. The possible reaction channels were found for the reaction. The reactions with triplet O3 were found to be the main reaction channels through the analysis of every reaction channel.The novel conclusions and ideas of this work are listed as follows:1. Classifications have carried on the isomerization mechanisms of (H)FNO+ and FNO2. The isomerization can be achieved in these ways: molecular partial rotation, gained isomers by atom migration, molecular relative vibration. Furthermor FNO2 isomers can be gained by omnibus mechanisms that the molecular framework recombined with atom migration or with molecular partial rotation.2. The charge density difference of molecule formation for (H)FNO+ isomers were made using GTA2000 program for the first time, the electron current was observed directly after FNO and FON protonated, the electron on H was increased, while the electron on F was reduced except (H)FNO+.3. The analysis for the typical reactions of the isomerization of (H)FNO+ and FNO2 by the topological analysis of electronic density indicates: some reactions experienced three-member ring transition region and structure transition state, while some reactions experienced four-member ring transition region and structure transition state. Not only planar structure but also non-planar structure was found in the four-member ring transition structure.4. Trough the analysis of the structure transition state and the energy transition state, we found that the three-member ring transition state, the planar four-member ring transition state and the non-planar four-member ring transition state were all consistent with the conclusion below: the structure transition state appeared after the energy transition state in the exothermic elementary reaction, while the structure transition state appeared before the energy transition state in the endothermic elementary reaction. It furtherconfirmed the conclusion propose by our group before, and also developed ourconclusion.