给／吸电子取代基对PPV类聚合物重组能影响的DFT研究

用密度泛函理论（density functional theory，DFF）在B3LYP／6—311G基组水平上对（PPV）4、（PPV）4-S进行结构全优化，计算得到了它们的重组能，讨论了不同给／吸电子取代基对PPV类电致发光聚合物重组能的影响．结果表明，给，吸电子取代基都使得PPV聚合物的重组能降低，性质相同的不同取代基对PPV类聚合物体系内电子离域范围影响程度不同，若取代基能参与主链轨道形成，使聚合物体系内电子离域范围增大，重组能降低更加明显，聚合物的传输速率增大；另一方面取代基的引入如果使得分子整体平面结构扭曲变形，则共轭效应相对减小，重组能降低数值减小．

THE THEORETICAL STUDY OF THE INFLUENCE OF DONOR/ACCEPTOR SUBSTITUTIONS TO THE REORGANIZATION ENERGY IN PPV - LIKE ELECTROLUMINESCENT POLYMERS

The geometries of phenylenevinylene and their ramifications have been optmized by using calculational method B3 LYP /6 - 311G. The influence of the reorganization energy on PPV - like electroluminescent polymers substituted by donor/acceptor substitutions is discussed . The reastdt indicates that, donor/acceptor substitutions all make the reorganization energy of PPV - like electroluminescent polymers decrease , different substitutions in the same nature has disparate conjugative effect, if the substitute group can participate in the principal chain track formation, it causes the territory scope of the polymer system, s electron enlarge, the reorganization energy λ reduces obviously, the hole transmission speed increases. Moreover the position of substitute group has something with the overall planar structure, if the planar structure distorts, the conjunctive effect reduces, then the reduction value of reorganization energy λ reduces.