双层石墨烯及相关修饰体系的结构、相互作用及非线性光学性质研究

In recent research on graphene-based non-linear optics (NLO) materials, significant progress has been made in a series of regulation strategies to enhancing the NLO responses of the mono-layer graphene systems.The double-layer graphene has not only the mono-layer's regulation strategies,but also the associative effects of the inter-layer regulation strategies. More importantly, the double-layer system has new structural factors such as the inter-layer distances and array patterns, etc. which are coming from the inter-layer interaction. In this project, the varied π/π interaction modes has been considered, and our invesigation aims at studying the structures, inter-layer interactions, inter-layer charge transfers, and the NLO properties of the double-layer graphenes and the relative modified systems by using quantum chemical methods;revealing the relationships among the inter-layer interactions, inter-layer charge transfers, and the NLO properties of the double-layer systems;exhibiting the new structural regulation strategies to the NLO responses, i.e. inter-layer distances and array patterns, etc, forming by the covalent and non-covalent π/π interaction and the other accompanying interaction such as hydrogen bond; summarizing the effects of the mono-layer systems' regulation strategies, including terminal substituent groups, excess electron(s) due to the doping alkali metal atom(s),heteroatom(s) into the framework,shape and defects of the graphenes, etc. and their inter-layer associative effects on the NLO responses.This research expands the new double-layer-graphene-based NLO material investigation field and will favor developing the new idea of the NLO material design in the double-layer graphene systems and suggesting potential and well-performance NLO materials with double-layer-graphenes.

最近在石墨烯类非线性光学(NLO)材料的研究中,单层体系的系列调控策略在提高其NLO响应方面取得了重要进展。双层石墨烯体系不但拥有单层体系的调控策略,还存在策略的层间组合效应,更重要的是具有层间相互作用产生的层间距和排列方式等新的结构调控因素。本项目考虑多种 π/π相互作用模式,用量化方法研究双层石墨烯及相关修饰体系的结构、层间相互作用、层间电荷转移及NLO性质;揭示其层间相互作用、层间电荷转移与NLO性质的关系;展示π/π相互作用(共价的和非共价的)及伴随的其它相互作用(如氢键等)产生的层间距和排列方式等新结构因素对NLO响应的调控规律;总结端基效应、碱金属掺杂形成额外电子、骨架引入杂原子、石墨烯形状及缺陷等单层调控策略及其层间组合效应对NLO响应的影响规律。本项目拓展了双层石墨烯体系的NLO研究新领域,有助于发展双层石墨烯类NLO材料的设计新思想,建议潜在的品优的双层石墨烯类NLO材料

对于非线性光学(NLO)分子材料来说,双层及多层石墨烯体系不但拥有单层体系的调控策略,还存在策略的层间组合效应,更重要的是由层间π/π相互作用产生的层间电荷迁移对NLO 响应有着显著的影响。本项目目的是用量化方法研究双层及多层石墨烯模型及相关修饰体系的结构、层间π/π相互作用、层间电荷迁移及NLO 性质;揭示其层间相互作用、层间电荷迁移与NLO性质的关系。虽然按项目计划得到的系列π/π石墨烯模型及相关修饰体系的NLO响应并不十分理想，但仍然展示了该类体系的层间电荷迁移、NLO性质及层间电荷迁移对NLO响应的影响规律；同时采用金属掺杂于双层或多层π/π相互作用体系，设计得到了系列高NLO响应的夹心化合物结构及该类体系的层间电荷迁移、NLO性质及层间电荷迁移对NLO响应的影响规律，部分体系中随着掺杂金属原子或者π薄片的位移展现了良好的NLO分子开关效应；另外在寻找层间电荷迁移体系的过程中，我们还得到了系列碱土金属掺杂的非π/π的电荷迁移作用体系的结构及相关性质，展示了电荷迁移对NLO响应的影响。我们认为，本项目拓展了双层及多层π/π电荷迁移作用体系的非线性光学分子材料研究新领域,有助于发展π/π层间电荷迁移作用类NLO 分子材料的设计新思想,建议潜在的品优的π/π层间电荷迁移作用NLO 分子材料。