低温Ar基质中CF_3I激光光氧化反应中间体研究  

Study on the Reaction Intermediates of Laser Induced Photooxidation of CF3I in Ar Matrix*

作　　者：陈末华[1] 王雪峰[1] 余敏[1] 秦启宗[1] 郑企克[1] 

机构地区：[1]复旦大学激光化学研究所

出　　处：《Chinese Journal of Chemical Physics》1998年第1期37-42,共6页化学物理学报（英文）

基　　金：国家自然科学基金

摘　　要：研究了１０ＫＡｒ基质中ＣＦ３Ｉ与Ｏ２经２６６ｎｍ脉冲激光辐照的光氧化反应，利用低温基质隔离技术和付里叶变换红外光谱法检测反应过程中产生的中间体有ＣＦ３ＯＯＩ、ＣＦ３ＯＯ、ＣＦ３Ｏ和ＣＦ３ＯＩ。通过量子化学从头算，对ＣＦ３ＯＯＩ的结构和振动频率进行计算，并对观察到的３个吸收峰进行了归属，首次确证ＣＦ３ＯＯＩ为新的中间体。根据ＣＦ３ＯＯ、ＣＦ３ＯＯＩ、ＣＦ３Ｏ、ＣＦ３ＯＩ随光照时间的生长和衰减，提出了ＣＦ３Ｉ在低温基质中的光氧化机理。Pulsed 266nm laser induced reaction of CF3I with O2 in Ar matrix has been studied by FTIR spectroscopy.Verification of the participation of CF3OOI as a reaction intermediate has been made for the first time in CF3I/O2 system.Equilibrium geometry,harmonic frequencies and their relative intensities have been calculated by ab initio calculation at the level of HF/LANLIDZ.Calculation results are in good agreement with experimental observations.Growth and decay of the IR absorption of CF3OO,CF3OOI,CF3O and CF3OI have been observed in the irradiation process,and provided experimental evidence for the reaction intermediates.A photooxidetion mechanism is proposed.

关 键 词：CF3I 激光光氧化 低温基质隔离 光氧化 中间体 

分 类 号：O621.146[理学—有机化学] O623.21[理学—化学]