荷移功能配合物的荷移机制与调控研究

On the basis of the modeling functional molecules which are related closely to the charge-transfer, several essential problems have been deeply explored in this project such as the structural properties of the donor-acceptor complexes, the coupling modes and interaction nature between the donor and the acceptor, the charge-transfer kinetics mechanism and its regulation, etc. The dependences of the charge-transfer quantities on the various factors are also determined. The resolved essential aspects include the structural and energetic characters of charge-transfer functional molecules, descriptions of the electronic states, the coupling modes and their interconversions, the multidimensional potential energy surfaces of the systems and the determination of the active parameters, the coupling matrix element between the active sites of donor and acceptor, the competition between charge transfer mechanism and other cooperating mechanisms and uniform calculational schemes for kinetic parameters. A continuous scale has been established between adiabatic and nonadiabatic behaviors of various kinetic parameters. The intrinsic relation of microscopic charge transfer with the macroscopically observed phenomena and properties, and the modulation-control schemes have been illustrated. Thus, this work has provided the necessary theoretical basis and methods for the applicable explorations of charge-transfer functional complexes.

用量子理论、统计理论、群论和分子力学等理论化学方法研究几类荷移功能分子的电荷转移机制与特征，给出各种相关量的精确确定方案及有关动力学公式；寻求各类分子自身与外界因素对电荷转移机理的影响，探讨诸类因素对荷移机理及荷移致分子功能性的调控作用，为进一步实施人工控制荷移反应、开发新型的功能材料提供必要的理论依据。