第一單元
假設離子液體中不同離子狀態間平衡時交換的速率太快以致於不能被NMR實驗分辨出來，且測量出來的陽離子對陰離子擴散比D+/D-，得到的擴散數據視為所有可能成分的整體數值，所表達的物理意義為：陰離子團聚物對陽離子團聚物的相對程度。這些數值會隨著溫度上升而下降，表示離子狀態轉為較小的離子團。在純的1-Butyl-3-methylimidazolium Hexafluorophosphate (BMI-PF6)， (BMI-PF6)nPF6- 陰離子團比(BMI-PF6)n BMI+陽離子團多，此種現象稱為 hyper anion preference (HAP)超陰離子傾向，也就是說，“BMI-PF6離子液體中自由陽離子數目比自由陰離子多”。此外，超陰離子傾向(HAP)也可用來解釋BMI-PF6/2,2,2-trifluoroethane (TFE)混合物以兩種不同莫耳分率組成 (XTFE = 0.65 和 0.80)的D+/D-和溫度相關值意義以及數種關於離子液體的物理性質：(1)陰離子擴散比陽離子擴散對溫度有較高的敏感度(2)陽離子轉移數目(Cationic Transference Number)隨溫度改變 (3)高ionicity和低ionic conductivity
(4)高黏度。

第二單元
利用核磁共振技術探討 BMI-PF6、BMI-BF4加入PEG系列溶劑後，以不同莫耳分率(0.05-0.5)，比較陰、陽離子的擴散速率變化。再利用得到的擴散速率D+/D-比值導出HAP(超陰離子傾向)，觀察離子液體的團聚行為。
我們認為離子狀態是影響擴散的主要因素：運用超陰離子的概念，解釋核磁共振觀測到的數據，可以幫助我們得到更多訊息。
結果顯示PEG溶劑分子的分子量和濃度愈大，愈不易形成超陰離子。即使陰陽離子在這些溶劑中的狀態有些不同，但還是超陰離子主導整個系統。

Assuming various ionic states in ionic liquids (ILs) are in equilibrium with exchange rates too high to be distinguished by NMR experiments and the overall response of measured diffusivity is viewed as the sum of weighted responses of diffusivity of all possible components, the ratio of cation diffusivity to anion diffusivity, D+/D–, in a specified IL affords the physical meaning: relative association degrees observed by anion-containing components to cation-containing components. These values decrease with increasing temperature showing the equilibrium between ionic states shifting to smaller components. In the neat 1-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF6), (BMI-PF6)nPF6– anions are found preferred to (BMI-PF6)nBMI+ cations and this phenomenon is termed as hyper anion preference (HAP). The HAP approach can be further employed to explain the temperature-dependent values of D+/D– obtained for BMI-PF6/2,2,2-trifluoroethane (TFE) mixtures at two different compositions (XTFE = 0.65 and 0.80), as well as numerous physical properties published for this IL: (1) higher sensitive of anionic diffusivity towards temperatures than cationic diffusivity, (2) temperature-dependent cationic transference number, (3) high ionicity and low ionic conductivity, (4) high viscosity.
1-butyl-3-methylimidazolium hexafluorophosp hate ( BMI-PF6 ) was mixed with various solvents such as PEG,PEI. The molar fraction of diluents were 0.05 to 0.5 and the nuclear magnetic resonance techniques were applied to investigate the influence of diffusion coefficient.
The most important factor between anions and cations on the diffusion coefficient are the ionic states. The state of hyper anion makes us easily know what happened to ionic interaction and ionic state.
The molecular weight and the concentration of PEG increase, it is not easier to generate hyperanion. Even if the anions and cations are a little different in these solvent, the hyper anions still play the most important role in these cosolvent systems.

第一單元
1. (a) Noda, A.; Hayamizu, K.;Watanabe, M. J. Phys. Chem. B 2001, 105, 4603-4610.
(b) Tokuda, H.; Hayamizu, K.; Ishii, K.; Susan, Md. A. B. H.; Watanabe, M. J. Phys. Chem. B 2004, 108, 16593-16600.
(c) Tokuda, H.; Hayamizu, K.; Ishii, K.; Susan, Md. A. B. H.; Watanabe, M. J. Phys. Chem.B 2005, 109, 6103-6110.
(d) Tokuda, H.; Ishii, K.; Susan, Md. A. B. H.; Tsuzuki, S.; Hayamizu, K.;Watanabe, M. J. Phys. Chem. B 2006, 110, 2833-2839.
(e) Tokuda, H.; Tsuzuki, S.; Susan, Md. A. B. H.; Hayamizu, K.; Watanabe, M. J. Phys. Chem. B 2006, 110, 19593-19600.
2. (a) Umecky, T.; Kanakubo, M.; Ikushima, Y. Fluid Phase Equilibria 2005, 228-229, 329-333.
(b) Umecky, T.; Kanakubo, M.; Ikushima, Y. J. Mol. liquids 2005, 119, 77-81.
3. (a) Hayamizu, K.; Aihara, Y.; Arai, S.; Martinez, C. G. J. Phys. Chem. B 1999, 103, 519-524.
(b) Hayamizu, K.; Aihara, Y.; Nakagawa, H.; Nukuda, T.; Price, W. S. J. Phys.
Chem. B 2004, 108, 19527-19532.
4. Block, F.; Hansen, W. W.; Packard, M.; Phys. Rev. 1946, 69, 127
5. Arnold, J. T.; Dharmatti, S. S.; Packard, M. E. J. Chem. Phys. 1951, 19, 507.
6. Yang, D.; Konrat, R.; Kay, L. E. J. Am. Chem. Soc. 1997, 119, 11938-11940.
7. Yang, D.; Kay, L. E. J. Am. Chem. Soc. 1999, 121, 2571-2575
8. Hsu, W. Y.; Tai, C. C.; Jen, K. C.; Chang, C. H.; Wang, S. P.; Sun, I. W. Inorg. Chim. Acta 2008, 361, 1281-1290.
9. Huang, J. F.; Chen, P. Y.; Sun, I. W.; Wang, S. P. Inorg. Chim. Acta 2001, 320, 7-11.
10. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M.A.;
Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A. Jr.; Stratmann, R. E.; Burant, J. C.; Dapprich, S.;Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.;
Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M.W.; Johnson, B.; Chen,W.;Wong, M.W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; Pople, J. A. Gaussian 98, Revision A.9, Gaussian, Inc., Pittsburgh PA, 1998.
11. (a) Vogel, H. Phys. Z. 1921, 22, 645.
(b) Fulcher, G. S. J. Am. Ceram. Soc. 1923, 8, 339-335.
(c) Tamman, G.; Hesse,W. Z. Anorg. Allg. Chem. 1926, 156, 245-257.
12.黃必瑋,國立成功大學化學研究所碩士論文, 2008.
13.許文一,國立成功大學化學研究所博士論文, 2007.

第二單元
1. Walden, P. Bull. Acad. Imper. Sci. 1914, 1800.
2. Wilkes, J. S.; Levisky, J. A.; Wilson, R. A.; Hussey, C. L. Inorg. Chem. 1982, 21, 1263-1264.
3. Giernoth, R. Ionic Liquids. 2009 , 290 , 263-283.
(a) Huang, J.F.; Chen, P.Y.; Sun, I. W.; Wang , S.P. Inorg Chim Acta 2001, 320, 7-11.
(b) Noda, A.; Hayamizu, K.; Watanabe, M. J Phys Chem B 2001, 105, 4603-4610.
(c) Hayamizu, K.; Aihara,Y.; Nakagawa, H.; Nukuda, T.; Price, W.S. J Phys Chem B 2004,108,19527-19532.
(d) Nicotera, I.; Oliviero, C.; Henderson, W.A.; Appetecchi, G.B.; Passerini, S. J. Phys. Chem. B 2005, 109, 22814-22819.
(e) Hayamizu, K.; Tsuzuki, S.; Seki, S.; Ohno, Y.; Miyashiro, H.; Kobayashi, Y.; J. Phys. Chem. B 2008, 112, 1189-1197.
(f) Tokuda, H.; Hayamizu, K.; Ishii, K.; Susan MABH.; Watanabe, M. J. Phys. Chem. B 2004, 108, 16593-16600.
(g) Chung, S. H.; Lopato, R.; Greenbaum, S.G.; Shirota, H.; Castner, E.W.; Wishart, J. F. J. Phys. Chem. B 2007, 111, 4885-4893.
(h) Noda, A.; Susan MABH.; Kudo, K.; Mitsushima, S.; Hayamizu, K.; Watanabe, M. J. Phys. Chem. B 2003, 107, 4024-4033.
(i) Iojoiu, C.; Judeinstein, P.; Sanchez, J.Y. Electrochim. Acta 2007, 53, 1395-1403.
(j) Judeinstein, P.; Iojoiu, C.; Sanchez, J.Y.; Ancian, B. J. Phys. Chem. B 2008, 112, 3680-3683.
(k) Palmer, G.; Richter, J.; Zeidler, M. D. Z. Naturforsch. A. Phys. Sci 2004, 59, 59-63
(l) Umecky, T.; Kanakubo, M.; Ikushima, Y. Fluid. Phase. Equilib 2005, 228, 329-333
4. Carpenter, J. E.; Weinhold, F. J. Mol. Struct. 1988, 169, 41-62.
5. Löwdin, P. O. Phys. Rev. 1955, 97, 1474-1489
6.(a)Tokuda,H.; Hayamizu, K.; Ishii, K.; Hasan Susan, Md. A. B.; Watanabe M.; J. Phys. Chem. B 2004, 108, 16593-16600.
(b)Tokuda, H.; Hayamizu, K.; Ishii, K.; Hasan Susan, Md. A. B.; Watanabe M. J. Phys. Chem. B 2005, 109, 6103-6110.
(c)Tokuda, H.; Ishii, K.; Hasan Susan, Md. A. B.; Tsuzuki, S.; Hayamizu,K.; Watanabe M. J. Phys. Chem. B 2006, 110, 2833-2839.
7.Umecky,T.; Kanakubo,M.; Ikushima,Y. Fluid. Phase. Equilibria 2005, 329, 228-229.
8. Wu, T. Y.; Wang, H. C.; Su, S. G.; Gung, S. T.; Lin, M. W.; Lin, C. B. Journal of the
Chinese Chemical Society 2010, 57, 44-55.
9. 黃必瑋, 國立成功大學化學研究所碩士論文,2008.
10. 許文一, 國立成功大學化學研究所博士論文,2007.