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采用密度泛函理论(DFT)研究卤素(F2,Cl2,Br2,I2,ICl)掺杂聚甲基苯基硅烷(PMPSi)的电子结构.在BH&HLYP/6-31G*水平上优化PMPSi,交错构象为最稳定构象.在此构象上优化卤素掺杂PMPSi并比较结构变化,进一步探讨复合物的前线轨道能量、吸收光谱等性质.结果表明,最高占据轨道(HOMO)的能量几乎保持不变,而最低空轨道(LUMO)的能量降低,能隙按Cl2>F2>ICl>Br2>I2顺序减小.以致电子由HOMO-1→LUMO跃迁,使复合物在吸收光谱中发生红移,在可见光区有较强的吸收峰.自然键轨道(NBO)理论分析表明电荷从主链向卤素转移.所有复合物经基组叠加误差(BSSE)校正后的相互作用能为-0.61～-3.20 kcal/mol,且掺杂剂的极性越大,复合物的相互作用能越大.并讨论掺杂剂位置对复合物的能隙和相互作用能的影响.该研究为PMPSi的相关研究提供理论线索和依据.
The electronic structure of poly (methylphenyl) silane (PMPSi) doped with halogens (F2, Cl2, Br2, I2 and IC1) was investigated by density functional theory (DFT). PMPSi was optimized at BH & HLYP / 6-31G * As the most stable conformation.However, the optimization of halogen-doped PMPSi in this conformation and the comparison of structural changes were carried out to further investigate the frontier orbital energy and absorption spectra of the composite.The results show that the energy of the highest occupied molecular orbital (HOMO) The energy of the LUMO decreases and the energy gap decreases in order of Cl2> F2> IC1> Br2> I2, resulting in the redox shift of the complex from the HOMO-1 → LUMO in the absorption spectrum. In the visible region (NBO). The theoretical analysis shows that the charge transfer from the main chain to the halogen.The interaction energies of all the complexes after BSSE correction are -0.61 ~ -3.20 kcal / mol , And the greater the polarity of the dopant, the greater the interaction energies of the complexes, and the influence of the dopant sites on the energy gap and interaction energies of the complexes is discussed. This study provides theoretical clues for the related studies of PMPSi and in accordance with.