用SAC-CI/6-311g方法计算了二甲基硅酮[DMS,(CH3)2SiO]的单重态和其激发态,得到基态为X1A1,其3个低激发态依次为1A2、1A1和1B1,其电子光谱都出现在紫外可见区,这是二甲基硅酮(DMS)的独特之点.根据群的对称性原理,指出在二甲基硅酮[DMS,(CH3)2SiO]中(图1),同时离解5H和8H,是对称性最许可的.计算出同时离解3C-5H和4C-8H时的离解能和同时离解键1Si-3CH3和1Si-4CH3时的离解能,由基H和CH3会发生自由基反应,这与脉冲辐射的紫外可见光谱无结构[3]的实验相合.可以预计在离解气体产物中,甲烷CH4成分最多,其次为H2,乙烷C2H6最少,文献[1]的实验正是如此.
参考文献
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