我們利用實驗室架設的克爾光閘超快時間解析螢光(time-resolved fluorescence, TRFL)光譜系統，搭配自行撰寫的一套全自動數據擷取電腦程式來探討電子給體-受體錯合物(electron donor-acceptor, EDA)的分子間電子轉移行為，利用錯合物的光譜資訊並搭配理論計算(Gaussian 09)的分析，並提出了可能的動力學模型。本論文研究的是四氰基乙烯-甲基苯取代錯合物(Tetracyanoethylene-Methylbenzene)溶於CH2Cl2及CCl4的電荷轉移(charge-transfer , CT)動力學，我們量測了TCNE-p-Xylene錯合物的光譜學行為，並配合實驗室前人對TCNE-Benzene、TCNE-Toluene的研究，綜合討論取代基對靜態、動態光譜的影響。另外，TCNE-p-Xylene擁有兩種構型，我們藉由調變激發波長來改變對不同構型的激發比例，一併分析了不同構型對光譜學的變化。我們測量靜態吸收光譜得到三種錯合物CT譜帶的位置，進而選定適當的激發波長激發錯合物的CT譜帶，並觀察錯合物在激發態中的TRFL光譜隨時間的變化。最後我們以總螢光強度(p(t))及平均放光頻率( (t))來分析錯合物在液相中，激發態的電荷再結合動態學。概括來講，錯合物經由初始激發至激發態後，伴隨快速的分子內轉換及結構緩解、震動緩解至較低能量的穩定態，接著發生電荷再結合完成一系列的電荷轉移動力學。動力學的擬合結果顯示，三種錯合物有著差不多的IC常數(< 0.2 ps)，但有著較為不同的CR速率(CH2Cl2: TCNE-Benzene 29 ps,TCNE-Tolulene 7 ps, TCNE-p-Xylene 0.5 ps ; CCl4 : TCNE-Benzene 150 ps,TCNE-Toluene 820 ps, TCNE-p-Xylene 290 ps )。另外三種錯合物在極性、非極性溶劑中的時間常數有著顯著落差，針對這兩種現象，我們大致利用電子給體的游離能及solvaiton來討論時間常數的差異，並考量電子偶合強度造成的影響。值得一提的是，本論文引進ISM(intersecting state model)的解釋，概略的分析了一系列TCNE-甲基苯取代錯合物在CCl4中，CR時間常數隨自由能的雙反轉趨。

This dissertation employed an ultrafast time-resolved fluorescence (TRFL) spectrometer implemented by optical Kerr gating (OKG) and density functional theory calculations implemented in the Gaussian 09 program to study electron transfer dynamics in tetracyanoethylene-methylbenzene (TCNE-MBZ) complexes (MBZ = Benzene, Toluene, p-Xylene) in two solvents (CH2Cl2, CCl4) of different polarities. We used femtosecond laser to excite the TCNE-MBZ complexes to the CT-states, and the resulting TRFL spectra were measured. Analyses of the total fluorescence intensity function P(t), which describes the temporal evolution of excited state population and transition dipole moment, revealed complex relaxations associated with charge recombination (CR). We found different decay behaviors in two solvents. The fastest component which are in the similar time scale (< 0.2 ps) for the three complexes is assigned to CT2→CT1 transition, and the slowest component is ascribed to CR. The CR time constants in CH2Cl2 for TCNE-p-Xylene, TCNE-Toluene, TCNE- Benzene are 0.5, 7 and 29 ps, respectively, The CR time constants in CCl4 for TCNE-p-Xylene, TCNE-Toluene, TCNE- Benzene are 290, 820 and 150 ps, respectively. We concluded that CR time constants are consisted with the behavior in the Marcus inverted region. However the CR rates in CCl4 is reverted when the driving force(-∆G0) increase in the case of TCNE-Benzene. We use the intersecting state model (ISM) to explain this unexpected behavior. ISM accounts for structural relaxation of complex which the Marcus theory does not consider. Finally, we found that the CR rates of complexes in polar solvent is faster than in nonpolar solvent,
which is mostly due to solvation effet.

第一章 序論 7
1-1 電子轉移概論 7
1-2 EDA錯合物概述 17
1-3 TCNE-p-Xylene文獻回顧 17
第二章 實驗系統與技術 32
2.1 超快飛秒雷射系統 32
2.1.1雷射產生源 33
2.1.2能量放大器 36
2.2 實驗技術 40
2.2.1 optical Kerr gating簡介 41
2.2.2時間解析克爾光閘螢光光譜儀實驗系統與組成 42
2.2.3 超快時間解析克爾光閘螢光光譜實驗自動化數據擷取系統 55
2.3 時間解析克爾光閘螢光光譜儀的校正 58
2.3.1 光譜靈敏度的校正 58
2.3.2 時間延遲(temporal delay)校正 65
2-5 EDA錯合物溶液的製備 69
2.5.1 TCNE的空白實驗 72
第三章 四氰基乙烯-對二甲苯錯合物之電荷轉移態研究 74
3-1 TCNE-甲基苯取代錯合物於CH2Cl2、CCl4溶劑中的靜態光譜 74
3-2 TCNE-甲基苯取代錯合物於CH2Cl2、CCl4中的時間解析螢光光譜 86
3-2.1 TCNE-甲基苯取代錯合物於CH2Cl2中的時間解析螢光光譜 87
3-2.2 TCNE-甲基苯取代錯合物於CCl4中的時間解析螢光光譜 103
3-3 TCNE-甲基苯取代錯合物的理論計算結果 116
3-3.1 基底態能量與結構 116
3-3.2 基底態的垂直激發躍遷計算 120
3-3.3 激發態能量與結構 126
3-4 綜合討論 130
3-4.1 螢光放光平均頻率 130
3-4.2 激發態的P(t)擬合參數探討 134
3-4.3 激發態的動態學模型 138
3-5 結論 144

Reference
1. Kamat, P. V., J. Phys. Chem. Lett 2012, 3 (5), 663-672.
2. Wegner, D.; Yamachika, R.; Wang, Y.; Brar, V. W.; Bartlett, B. M.; Long, J. R.; Crommie, M. F.,Nano lett 2008, 8 (1), 131-5.
3. Gilbert, M.; Albinsson, B., Chem. Soc. Rev 2015, 44 (4), 845-62.
4. Nicolet, O.; Banerji, N.; Pages, S.; Vauthey, E., J. Phys. Chem. A 2005, 109 (37), 8236-45.
5. Varandas, A. J. C.; Formosinho, S. J., J. Chem. Soc, Chemical Communications 1986, (2), 163.
6. Serpa, C.; Gomes, P. J.; Arnaut, L. G.; Formosinho, S. J.; Pina, J.; de Melo, J. S., Chemistry 2006, 12 (19), 5014-23.
7. Mohammed, O. F.; Adamczyk, K.; Banerji, N.; Dreyer, J.; Lang, B.; Nibbering, E. T.; Vauthey, E., Angewandte Chemie 2008, 47 (47), 9044-8.
8. Ito, F.; Nagamura, T., J J Photochem. Photobiol. C: Photochem. Rev 2007, 8 (4), 174-190.
9. Mulliken, R. S., J. Phys. Chem. 1952, 56 (7), 801-822.
10. Leonhardt, H.; Weller, A., Z. Phys. Chem. 1961, 29 (3_4), 277-280.
11. Kroll, M., J.Am. Chem. Soc 1968, 90 (5), 1097-1105.
12. Hanazaki, I., J. Phys. Chem 1972, 76 (14), 1982-1989.
13. Prochorow, J., J. Chem. Phys 1966, 44 (12), 4545.
14. Mobley, M. J.; Rieckhoff, K. E.; Voigt, E. M., J. Phys. Chem 1977, 81 (8), 809-810.
15. Holder, D. D.; Thompson, C. C., J. Chem. Soc, Chemical Communications 1972, (5), 277b.
16. Russell, T. D.; Levy, D. H., J. Phys. Chem 1982, 86 (14), 2718-2727.
17. Prochorow, J., J Lumin 1974, 9 (2), 131-142.
18. Vincent, V. M.; Wright, J. D., J. Chem. Soc, Faraday Transactions 1: Physical Chemistry in Condensed Phases 1974, 70 (0), 58.
19. Rubtsov, I. V.; Yoshihara, K., J. Phys. Chem. A 1999, 103 (49), 10202-10212.
20. Dillon, R. J.; Bardeen, C. J., J. Phys. Chem. A 2011, 115 (9), 1627-33.
21. Rubtsov, I. V.; Yoshihara, K., J. Phys. Chem. A 1999, 103 (49), 10202-10212.
22. Roberts, G. M.; Lecointre, J.; Horke, D. A.; Verlet, J. R., PCCP 2010, 12 (23), 6226-32.
23. Fleming, G. R., Chemical Applications of Ultrafast Spectroscopy Oxford: New York, 1986.
24. Lakowicz, J. R., Principles of Fluorescence Spectroscopy. 2nd ed.; Plenum Press: New York, 1999.
25. Boyd, R. W., Nonlinear Optics. Academic Press: San Deigo, CA, 1992.
26. Moxtek http://www.moxtek.com/optics/visible_light.html.
27. Kalpouzos, C.; Lotshaw, W. T.; McMorrow, D.; Wallace, G. A. K., J. Phys. Chem. 1987, 91.
28. Kinoshita, S.; Ozawa, H.; Kanematsu, Y.; Tanaka, I.; Sugimoto, N.; Fujiwara, S., Rev. Sci. Instrum. 2000, 71 (9), 3317-3322.
29. Marcus, Y., The Properties of Solvents. John Wiley: Sons, New York, 1998.
30. Neelakandan, M.; Pant, D.; Quitevis, E. L., Chem. Phys. Lett. 1997, 265.
31. Weber, M. J., Handbook of Optical Materials. CRC Press: Boca Raton, FL, 2003.
32. Kalpouzos, C.; Lotshaw, W. T.; Mcmorrow, D.; Kenneywallace, G. A., J. Phys. Chem. 1987, 91 (8), 2028-2030.
33. Takeda, J.; Nakajima, K.; Kurita, S.; Tomimoto, S.; Saito, S.; Suemoto, T., Phys Rev B 2000, 62 (15), 10083-10087.
34. Schmidt, B.; Laimgruber, S.; Zinth, W.; Gilch, P., Appl. Phys. B Lasers Optic 2003, 76 (8), 809-814.
35. Arzhantsev, S.; Maroncelli, M., Appl. Spectrosc 2005, 59 (2), 206-220.
36. Andor http://www.andor.com/pdfs/specs/du970n.pdf.
37. Gardecki, J. A.; Maroncelli, M., Appl. Spectrosc 1998, 52 (9), 1179-1189.
38. Bevinton, P. R.; Robinson, D. K., Data Reduction and Error Analysis for the Physical Sciences. McGraw-Hill: New York, 1992.
39. CVI http://www.cvimellesgriot.com/glossary/imagesDir/016.gif.
40. Wynne, K.; Galli, C.; Hochstrasser, R. M., J. Chem. Phys. 1994, 100 (7), 4797-4810.
41. Frey, J. E.; Andrews, A. M.; Ankoviac, D. G.; Beaman, D. N.; Dupont, L. E.; Elsner, T. E.; Lang, S. R.; Zwart, M. A. O.; Seagle, R. E.; Torreano, L. A., J. Org. Chem. 1990, 55 (2), 606-624.
42. Ewall, R. X.; Sonnessa, A. J., J. Am. Chem. Soc. 1970, 92 (9), 2845-&.
43. Fraser, R. D. B.; Suzuki, E., Anal.Chem 1969, 41 (1), 37-39.
44. Lippert, E., Z Naturforsch Pt A 1955, 10 (7), 541-545.
45. Mataga, N.; Kaifu, Y.; Koizumi, M., Bull. Chem. Soc. Jpn. 1955, 28 (9), 690-691.
46. Mataga, N.; Kaifu, Y.; Koizumi, M., Bull. Chem. Soc. Jpn. 1956, 29 (4), 465-470.
47. Lippert, E., Zeitschrift Fur Elektrochemie 1957, 61 (8), 962-975.
48. Reynolds, L.; Gardecki, J. A.; Frankland, S. J. V.; Horng, M. L.; Maroncelli, M., J. Phys. Chem. 1996, 100 (24), 10337-10354.
49. Jarzeba, W.; Murata, S.; Tachiya, M., Chem. Phys. Lett. 1999, 301 (3-4), 347-355.
50. Laurence, C.; Nicolet, P.; Dalati, M. T.; Abboud, J. L. M.; Notario, R., J. Phys. Chem. 1994, 98 (23), 5807-5816.
51. Kamlet, M. J.; Abboud, J.-L. M.; Abraham, M. H.; Taft, R. W., J. Org. Chem. 1983, 48, 2877-2887.
52. Horng, M. L.; Gardecki, J. A.; Papazyan, A.; Maroncelli, M., J. Phys. Chem.1995, 99 (48), 17311-17337.
53. Larsen, D. S.; Ohta, K.; Fleming, G. R., J. Chem. Phys. 1999, 111 (19), 8970-8979..
54. Zhao, Y.; Truhlar, D. G., J. Phys. Chem. A 2006, 110 (49), 13126-13130.
55. Kysel, O.; Budzak, S.; Mach, P.; Medved, M., Int. J. Quantum Chem 2010, 110 (9), 1712-1728.
56. Kuchenbecker, D.; Jansen, G., Chemphyschem 2012, 13 (11), 2769-2776.
57. Mach, P.; Budzák, Š.; Medveď, M.; Kyseľ, O., Theoretical Chemistry Accounts 2012, 131 (9).
58. Arnold, B. R.; Farid, S.; Goodman, J. L.; Gould, I. R., J. Am. Chem. Soc 1996, 118 (23), 5482-5483.
59. Arnold, B. R.; Noukakis, D.; Farid, S.; Goodman, J. L.; Gould, I. R., J. Am. Chem. Soc 1995, 117 (15), 4399-4400.