自由基聚合中二硫酯结构及其活性的研究

Study on the structure and activity in thiocarbonylthio compounds for radical polymerization

用密度泛函方法,在B3LYP/6-31G+(d)水平上对三种二硫酯化合物进行了几何构型全优化.计算了C-S键离解能以及对于自由基的原子自旋密度,并且探讨了它们与化合物活性之间的关系,分析的结论与实验结论完全一致.同时结论也表明密度泛函理论计算能为C—S键离解能,原子自旋密度变化趋势提供一个很好的预测.

The structures of three thiocarbonylthio compounds were optimized with B3LYP methods at 6- 31G＋ （d） level. We calculated C--S bond dissociation energies（BDE）, and atomic spin densities for radicals, the correlation between these data and activity of these three compounds were explored. The final results are good agreement with the experimental conclusions. In addition, our results demonstrated that density functional theory （DFT） can provide a good prediction of the trends in C--S BDE and atomic spin densities for radicals.