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采用密度泛函理论中的广义梯度近似(DFT/GGA)方法,在PW91/DNP水平上研究了4,7-二(2-噻吩基)苯并噻二唑-3-辛基噻吩二炔在PdCl2(PPh3)2催化下的合成机理.优化了反应过程中的反应物、中间体、过渡态和产物,通过能量分析结果证实了中间体和过渡态的真实.在同样的方法和精度研究了4,7-二(2-噻吩基)苯并噻二唑-3-辛基噻吩二炔在没有催化剂下的合成机理.通过计算结果得到此反应在有PdCl2(PPh3)2催化情况下的活化能小于没有催化剂情况下的活化能,从而证明了PdCl2(PPh3)2催化剂的催化活性.采用密度泛函理论与周期性平板模型相结合的方法,研究了产物P在TiO2(100)表面的吸附,通过Mulliken charge和前线轨道分析表明:当P吸附在TiO2(100)表面时,P向TiO2(100)表面转移0.692 e电荷,前线轨道能隙变窄.理论预测的结果与实验值吻合.
Using the generalized gradient approximation (DFT / GGA) method in density functional theory (DFT), the effect of 4,7-bis (2-thienyl) benzothiadiazole- PdCl2 (PPh3) 2catalyzed the reaction mechanism, the intermediate, the transition state and the product were optimized, and the results of energy analysis confirmed the authenticity of intermediate and transition state.In the same method and precision studied Synthesis mechanism of 4,7-bis (2-thienyl) benzothiadiazole-3-octythiophenediyne in the absence of catalyst The activation of this reaction in the presence of PdCl2 (PPh3) 2 was obtained by calculation The catalytic activity of PdCl2 (PPh3) 2 catalyst was proved to be lower than that of the PdCl2 (PPh3) 2 catalyst. The adsorption of P on the surface of TiO2 (100) was investigated by means of density functional theory and periodic plate model Mulliken charge and frontier orbital analysis show that when P is adsorbed on the surface of TiO2 (100), P can transfer 0.692 e charge to the surface of TiO2 (100), and the frontier orbital energy gap becomes narrower.The theoretical predictions are consistent with the experimental data.