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本文综述了离子型液体介质中过剩电子的结构、存在状态及其时间演化动力学特征。基于从头算分子动力学模拟及计算结果,重点阐述了咪唑型、吡啶型、碱金属离子型熔盐氯化物离子液中与过剩电子溶剂化密切相关的溶剂化能量学、结构特征、可能的存在状态以及态-态转化稳态动力学机制,分析了此类离子型介质中电子高效传导的内在本质及离子液组成离子的重要作用。阳离子的最低未占轨道组成的导带结构是离子液中过剩电子的溶剂化态及其稳定性的决定因素,任何能影响或改变其导带结构的因素均能显著影响过剩电子溶剂化。但快速的态-态转化及电子迁移并不明显取决于其组成离子扩散动力学,而是敏感地受离子液涨落所控制。这种基于溶剂化电子的迁移模式构成了此类离子型介质甚至其他液态介质中电子转移的新途径。
This review summarizes the structure, state of existence and time evolution kinetics of excess electrons in ionic liquids. Based on ab initio molecular dynamics simulations and calculations, the energetic energetics, structural characteristics and possible existences of solvatochromic ionic liquids with imidazole, pyridine and alkali metal ions in molten salt chloride ionic liquids are emphatically elaborated State and steady-state kinetics of state-state transformation, and analyzes the intrinsic nature of electron-efficient conduction in such ionic media and the important role of ionic liquid ions. The conduction band structure of the lowest unoccupied orbitals of the cation is the determinant of the solvatisation and stability of the excess electrons in the ionic liquid. Any factors that can influence or change the conduction band structure can significantly affect the excess electron solvation. However, rapid state-to-state transition and electron transfer do not significantly depend on their composition of ion diffusion kinetics, but rather are sensitively controlled by ionic liquid fluctuations. This solvent-based electron-based migration pattern constitutes a new approach for electron transfer in such ionic media and even in other liquid media.