有機芳香胺化合物已被廣泛使用於電洞傳輸材料，為了能有效設計一個高效率且具令人滿意的電荷傳輸性質的電致發光材料，一系列化合物的電洞的遷移速率和重組能透過Marcus理論被計算研究。本論文所有的化合物均以全始算中的DFT b3LYP/6-31G*計算方法計算。本論文主要包含二部分:第一部分是電洞傳輸材料的重組能研究，而第二部分為TPA和PC分子在游離能和重組能方面的取代基取代效應。 首先在第一部分中，十五個芳香胺化合物分子和陽離子的結構被最佳化計算，再以此最佳化結構計算出化合物酌重組能和游離能，由研究的結果可得: 芳香胺化合物的重組能由其HOMO能階的電子雲密度分佈所影響。 在第二部分研究中發現: TPA和PC分子的衍生物計算所得的游離能和重組能，能被取代基的Hammett係數( σ and σ+)影響，且計算所得的游離能與重組能和取代基的Hammett係數存在良好的線性關係。在此部分研究中，取代基效應對游離能與重組能亦被討論，HOMO能階、游離能與重組能的趨勢也透過Hammett係數被探討，希望經由此方法能進一步設計出新的電洞材料。 在實驗中，雖然大部分化合物的物理和光學性質已被研究，但期望藉由理論的計算研究方法開發出新的光電材料。 The organic compounds with amino group have been used widely as the hole-transporting EL materials. To pursue the efficient OLEDs with desirable charge carrier transport property, the mobilities and reorganization energies for hole-transporting in a series of compounds were studied computationally based on the Marcus electron transfer theory with the ab initio DFT B3LYP/6-31G* calculated. This thesis comparises two parts: 1. the reorganization energy of the hole-transporting in organic compounds with amino group in the OLED were studied. 2. the substitution effect in triarylamines (TPA) and 9-Phenyl-9H-carbazole (PC) with different substituents were studied. According to the calculation results, one may conclude that the reorganization energy of these compounds are related to their electronic density of the HOMO state. The first part of this thesis, the geometries of 15 organic compounds in neutral and cationic states were optimized. Their reorganization energies and ionization potentials were calculated base on these optimized structures. Part two of this thesis, the calculated Ip and reorganization energy of hole-transporting for a series of TPA and PC compounds have been corrected with their experimental Hammett parameter (σ and σ+). The substituted effects in these compounds were investigated also. We also evaluated the reorganization energies of these compounds and investigated the substitutent effect in these compounds. Furthermore, the calculation procedure may estimate the trend of HOMO energies, Ip and reorganization energies for hole transport. These compound could be extended to the molecular design of new hole-transporting and EL materials. Although most of physical properties of the molecular were studied experimentally, the theoretical calculations provide enough to predict possible electrophysical properties in the development EL material.
