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采用密度泛函方法在(U)B3LYP/6-3 1+G(d,p)水平上对含咪唑与TEMPO单元的离子液体(TEMPO-IL)及其得失电子后的情况进行理论研究。通过设计氧化还原反应、利用吉布斯自由能变,计算了不同型体组成电对的电势数值,用以阐明型体结构与其属性的关系。结果表明:(1)TEMPO-IL得一个电子后的三线态Triplet-Ⅱ比单线态Singlet-Ⅱ稳定;(2)TEMPO-IL得一个电子的过程明显影响了咪唑端的键长与自然电荷布居:继续得一个电子后,受到明显影响的是自由基端。另一方面,当TEMPO-IL失去一个电子时,仍然是自由基端发生明显变化:(3)TEMPO-IL的正电荷布居在C2上,而非人们通常认为的N3上:(4)计算得到的TEMPO-IL不同型体的氧化还原电对的电势数值分别为-5.51V、-0.32V、4.19V,利用电势数值可对实验中存储装置测得的写电压(-6V)、读电压(-1V)、擦电压(5V)进行合理解释,这些计算结果表明存储装置的读、擦、写电压与TEMPO-IL得失电子的型体结构变化有直接关系。这些计算结果可为开发新型存储材料提供有用的理论参考。
The density functional theory (TEM) method was used to study TEMPO-IL with and without electrons at (U) B3LYP / 6-3 1 + G (d, p) By designing the redox reaction and using the Gibbs free energy change, the potential values of different types of compositional pairs are calculated to clarify the relationship between the type structure and its properties. The results showed that: (1) Triplet-II triplet after TEMPO-IL had one electron was more stable than single-state Singlet-Ⅱ; (2) TEMPO-IL had an obvious effect on the bond length and natural charge of imidazole : Continue to get an electron, was significantly affected by the free radical end. On the other hand, when TEMPO-IL loses an electron, there is still a significant change in the free-radical end: (3) the positive charge of TEMPO-IL resides on C2 rather than the one commonly thought of as N3: (4) The obtained TEMPO-IL different types of redox couple potential values were -5.51V, -0.32V, 4.19V, the potential value of the experimental storage device can be measured write voltage (-6V), read voltage (-1V) and erase voltage (5V). These calculations show that the reading, erasing and writing voltages of the memory device are directly related to the structural changes of TEMPO-IL gain and loss electrons. These results can provide a useful theoretical reference for the development of new storage materials.