Mechanism and efficiency of photochemical transformation of ¡ÔSiNNO?radicals grafted to activated Aerosil surface: Calculation of potential energy surface elements for the lower excited state of the radical

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• 作者：V. I. Pergushov and M. Ya. Mel¡¯nikov
• 刊名：High Energy Chemistry
• 出版年：2008
• 出版时间：November, 2008
• 年：2008
• 卷：42
• 期：6
• 页码：442-445
• 全文大小：212.6 KB

文摘

Assignment of the bands in the optical absorption spectrum of ≡SiNNO• radicals grafted to activated Aerosil surface was performed. A photochemical transformation mechanism was proposed, and the quantum yields of the reaction of ≡SiNNO• radicals relevant to the long-wavelength absorption band at 77 K were determined in the absence and presence of adsorbed CO₂ and SF₆ on the surface. For the model radical F₃SiNNO•, the parameters characterizing the equilibrium geometry of excited states and the geometry of transition states involved in the reaction were determined by quantum-chemical calculations.