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博碩士論文 etd-0110108-093918 詳細資訊
Title page for etd-0110108-093918
論文名稱
Title
含雜環硬桿式分子第一超極化率之計算分析
Computational analysis of first hyperpolarizability of heterocyclic rigid-rod molecules
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
68
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2007-12-19
繳交日期
Date of Submission
2008-01-10
關鍵字
Keywords
非線性光學、第一超極化率、密度泛函理論
nonlinear optics, first hyperpolarizability, DFT
統計
Statistics
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中文摘要
本研究針對含5-6-5雜環硬桿式發色團分子(5-6-5 heterocyclic rigid-rod chromophores) 的衍生物之二次非線性光學效應中的第一超極化率β(first hyperpolarizability) ,使用第一原理 (first principle)的CASTEP軟體與半經驗式的MOPAC軟體來計算發色團的光學性質,並作有系統的計算分析。共分成四個因素來設計並計算發色團: (i)三類雜環硬桿式分子,(ii)五員雜環的輔助能力,(iii)推電子基的能力,以及(iv)共軛長度的因素。
計算結果顯示含benzobisimidazole (BBI)的衍生物之β比起含benzobisthiazole (BBT)和benzobisoxazole(BBO)的β還大,吡咯(pyrrole)對施體的輔助能力比噻吩(thiophene)和呋喃(furan)高。推電子基強度正比於β,且其趨勢為-N(CH3)2 > -NH2 > -OH > -CH3。而共軛長度也是正比於β。此外從能帶解析 (band-resolved)β圖以及軌域密度(orbital density)圖可以得知主要貢獻於β的部份是從施體經由雜環架橋到受體的電荷轉移。最後比較兩類計算方法可以發現半經驗式的方法並不適用於計算多環化合物。
Abstract
The first hyperpolarizability β, which is an important factor in the second-order nonlinear optical effect, of the 5-6-5 heterocyclic rigid-rod chromophores-based derivatives has been systematically investigated in this work, applying the first principle based software CASTEP and the semi-empirical software MOPAC There are four factors chosen for this computational analysis, including the effects of (i) various rigid-rod molecules, (ii) auxiliary ability of various five-member rings, (iii) donor ability, and (iv) conjugation length.
Results indicate that the benzobisimidazole (BBI)-based derivatives have larger β values than those of benzobisthiazole (BBT) and benzobisoxazole (BBO)-based derivatives. The auxiliary donor ability of the pyrrole is larger than that of the thiophene and furan. In general, the β value of various derivatives studied is parallel to the original donor strength and the trend in the donor is -N(CH3)2 > -NH2 > -OH > -CH3. In addition, the greater the conjugation length in the derivatives is, the higher the β value. Further, from the analyses on the band-resolved β values and the orbital density figures, it is found that the major contribution to the enhanced β comes primarily from an efficient charge transfer from the donor side via the intermediate heterocyclic bridge to the acceptor side. Finally, a comparison between CASTEP and MOPAC reveals that CASTEP is more appropriate and accurate in predicting the optical properties of the heterocyclic-ring-based derivatives.
目次 Table of Contents
致 謝 i
摘 要 ii
Abstract iii
目 錄 iv
圖索引 vi
表索引 vii

第一章 緒論 8
1.1 前言 8
1.2 研究動機 8

第二章 文獻回顧 10
2.1 非線性光學 10
2.1.1 非線性光學簡介 10
2.1.2 非線性光學材料 14
2.1.3 有機非線性光學材料之設計 22
2.2 量子力學 28
2.3 密度泛函理論 28
2.4 光學性質 28

第三章 研究方法 36
3.1 硬體設備及軟體 36
3.1.1 硬體設備 36
3.1.2 使用軟體 36
3.2 計算第一超極化率所使用之理論公式 39

第四章 結果與討論 41
4.1 共軛硬桿狀雜環芳香族分子 41
4.2 不同雜環架橋之影響 46
4.3 推電子基強度 50
4.4 使用烯基延長分子長度之比較 55
4.5 綜合討論 55

第五章 結論與未來工作 58
參考文獻 59
附錄A 密度泛函理論相關公式推導 61
參考文獻 References
1. 陳建汎, 含苯并雙比唑之聚合物的合成與鑑定分析,國立中山大學博士論文,2004.
2. 邱子維, 新型二次非線性光學用聚羥基醯亞胺之合成與鑑定,國立中山大學碩士論文, 2004.
3. 吳受勳, 含苯并雙噻唑之二次非線性光學聚醯亞胺的合成與鑑定, 國立中山大學碩士論文, 2005.
4. 陳烜平, 新型含苯并雙噻唑之二次非線性光學聚醯亞胺的合成與鑑定,國立中山大學碩士論文, 2007.
5. Franken, P. A.; Hill, A. E.; Peters, C. W.Weinreich, G., Phys. Rev. Lett 1961, 118, 7.
6. Prasad, P. N. Williams, D. J., Introduction to Nonlinear Optical Effects in Molecules and Polymers, John Wiley and Sons, 1991.
7. Kanis, D. R.; Ratner, M. A.; Marks, T. J. Chem. Rev. 1994, 94, 195.
8. Mark, G. K.; Carl, W. D., Characterization Techiques for Organic Nonlinear Optical Materials, Marcel Dekker, 1998.
9. Zumsteg, F. C.; Bierlein, J. D.; Gier, T. E. J.Appl. Phys. 1976, 47, 4908.
10. Chen, C. T.; Wu, Y. C.; Jiang, A. D.; Wu, B. C.; You, G. M.; Li, R. K.;Lin, S. J. J. Opt. Soc. Am. B 1989, 6, 616.
11. Levine, B. F.; G.Bethea, C.; Thurmobd, C. D.; Lynch, R. T.; Bernstein, J. L. J. Appl. Phys. 1979, 50.
12. Lipscomb, G. F.; Garito, A. F.; Narang, R. S. J. Chem. Phys. 1981, 75.
13. Zyss, J.; Chemla, D. S.; Nicoud, J. F. J. Chem. Phys. 1981, 74, 4800.
14. Ziolo, R.; Gunter, W. H. H.; Meredith, G. R.; Williams, D. J. Acta Crystallogr. Sect. B 1982, 38, 341.
15. Min, Y. H.; Lee, K. S.; Yoon, C. S.; Do, L. M. J. Mater. Chem. 1998, 8, 1225.
16. Min, Y. H.; Mun, J.; Yoon, C. S.; Kim, H. K.; Lee, K. S. Electron. Lett. 1999, 35, 1770.
17. Kajzar, F.; Lee, K. S.; Jen, A. K.-Y. Advances Polymer Science 2003, 161, 1.
18. Oudar, J. L.; Chemla, D. S. Opt. Commun. 1975, 13, 164.
19. Oudar, J. L.; Chemla, D. S. J. Chem. Phys. 1977, 66, 2664.
20. Chemla, D. S.; Zyss, J. Nonlinear optical properties of organic molecules and crystals, Academic Press, Orlando, 1987.
21. Zyss, J. Molecular nonlinear optics: materials, physics and devices; Academic Press,Boston, 1994.
22. Levine, B. F.; Bethea, C. G. J. Chem. Phys. 1975, 63, 2666.
23. Oudar, J. L. J. Chem. Phys. 1977, 67, 446.
24. Dulcic, A.; Sauteret, C. J. Chem. Phys. 1978, 69, 3453.
25. Katz, H. E.; Singer, K. D.; Sohn, J. E.; Dirk, C. W.; King, L. A.; Gordon, H. M. J. Am. Chem. Soc. 1987, 87, 6561.
26. Oudar, J. L.; LePerson, H. Opt. Commun. 1975, 15, 258.
27. Dulcic, A.; Flytzanis, C.; Tang, C. L.; Pepin, D.; Fitzon, M.; Hoppiliard, Y. J. Chem. Phys. 1981, 74, 1559.
28. Morley, J. D.; Docherty, V. J.; Pugh, D. J. Chem. Soc. Perkin Trans 1987, 2, 1351.
29. Barkovig, G.; Shen, Y. R.; Schadt, M. Mol. Cryst. Liq. Cryst. B 1987, 150, 607.
30. Cheng, L. T.; Tam, W.; Stevenson, S. H.; Meridith, G. R.; Rikken, G.; Marder, S. R. J. Phys. Chem. 1991, 95, 10631.
31. Cheng, L. T.; Tam, W.; Marder, S. R.; Steigman, A. E.; Rikken, G.; Spangler, C. W. J. Phys. Chem. 1991, 95, 10643.
32. Rao, V. P.; Jen, A. K-Y.; Wong, K. Y.; Drost, K. J. Tetrahedron Lett. 1993, 34, 1747.
33. Jen, A. K-Y.; Rao, V. P.; Wong, K. Y.; Drost, K. J. J. Chem. Soc., Chem. Commun. 1993, 90.
34. Wong, K. Y.; Jen, A. K-Y.; Rao, V. P. Phys. ReV. A 1994, 49, 3077.
35. Rao, V. P.; Cai, Y.; Jen, A. K-Y. J. Chem. Soc., Chem. Commun. 1994, 1689.
36. Wong, K. Y.; Jen, A. K-Y.; Rao, P. V.; Drost, K. J. J. Chem. Phys. 1994, 100, 6818.
37. Jen, A. K-Y.; Rao, V. P.; Chandrasekhar, J. In Polymers for Second Order Nonlinear Optics; Lindsay, G. A., Singer, K. D., Eds.; ACS
Symposium Series 601; American Chemical Society: Washington, DC,
1995.
38. Varanasi, P. R.; Jen, A. K-Y.; Chandrasekhar, J.; Namboothiri, I. N. N.; Rathna, A. J. Am. Chem. Soc. 1996, 188, 12443.
39. Israel, D. L. A.; Tobin, J. M.; Mark, A. R. J. Am. Chem. Soc. 1997, 119, 6575.
40. Koch, W.; Holthausen, M. C. A chemist's guide to density functional theory, 2nd edition, Wiley-VCH, 2001.
41. Meier, H. Angew. Chem. 2005, 44, 2482.
42. Godby, R. W.; Schluter, M.; Sham, L. J. Phys. ReV. B 1988, 37, 10159.
43. Wang, C. S.; Klein, B. M. Phys. ReV. B 1981, 24, 3417.
44. Lin, J.; Lee, M.-H.; Liu, Z.-P.; Chen, C. T.; Pickard, C. J. Phys. ReV. B 1999, 60, 13380.
45. Rashkeev, S. N.; Lambrecht, W. R. L.; Segall, B. Phys. ReV. B 1998, 57, 3905.
46. Lee, M.-H.; Yang, C. H.; Jan, J. H. Phys. ReV. B 2004, 70, 235110.
47. Lee, S. H.; Otomo, A.; Nakahama, T.; Yamaka, T.; Kamikado, T.; Yokoyama, S.Mashiko, S., J. Mater. Chem. 2002, 12, 2187.
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