Theoretical prediction of new noble-gas containing anions

• Main Authors: Yi-hung Chang, 張義鴻
• Other Authors: Wei-Ping Hu
• Format: Others
• Language: zh-TW
• Published: 2006
• Online Access: http://ndltd.ncl.edu.tw/handle/01611834411848335378

碩士 === 國立中正大學 === 化學所 === 94 === In chapter one, the structures and energies of the noble-gas containing anions F-(NgO)n n =1~ 6 ( Ng = He, Ar, Kr )have been calculated by high-level ab initio calculation.The F - Ng bonds were increased by 0.07 Å for gradually increase NgO. The reaction energies of dissociation pathways F-(NgO)n→F-+ n Ng + n O(S)，energies increased by 13 ~ 60 kcal/mol for gradually increase NgO. We find that there are many O=Ng bond ligands around anion F-. The reaction energy is large, and the singlet-state is stable. In chapter two of this thesis, high-level electronic structure calculation has been performed on the noble-gas molecules F-NgY ( Ng = He, Ar, Kr Y= BN, BeO). For F-KrBN the high-level calculation shows that the reaction energies of dissociation pathways, (1) FNgY-→ F-+ Ng + Y, and (2) FNgY- → FY- + Ng is -58.3 and 89.2 kcal/mol and barriers of the pathways (1) is 19.1 kcal/mol, respectively. For F-KrBeO the reaction energies are -55.2 and 83.1 kcal/mol and barriers of the pathways (1) is 7.0 kcal/mol. The population analysis indicates the covalent of the Ng-Y bond. The calculated results shows the F-KrY (Y= BN, BeO) could be dynamically stable species. In chapter three, ab initio electronic calculations provide potential energy surfaces for CF3CFHO reaction with O2. Additional calculations with the same methods study the analogous reactions of the unfluorinated analogue CH3CH2O. We have used multi-coefficient Gaussian-3(MCG3) with multi-level electronic structure methods (MLSEn+d) for calaulated potential energy surfaces.We show that CF3CFHO reacts more rapidly with O2 than its unfluorinated analogue, CH3CH2O. But CH3CH2O in the experiment is rapidly. The computations presented here do suggest that CH3CH2O reacts more rapidly with O2.