偶氮二苯胺的合成表征、光折变性质及理论研究
|
摘要
本文合成了二阶非线性光学生色分子N-(对硝基苯偶氮)-苯胺基苯(AZOPA)，并进行了必要的结构表征，同时测定了它的光折变性质，研究结果表明，以以AZOPA为二阶非线性生色团，PVK(聚乙烯咔唑)为电荷传输体，TNF(三硝基芴酮)为光敏剂，并添加PBA(聚丙烯酸丁酯)为增塑剂的复合物在不加外电场时就可以观察到光折变效应。其二波耦合系数达到140cm~(-1)，衍射效率近4％。在外加低电场(25V／μm)时，其二波耦合系数达到470cm~(-1)，衍射效率近10％。这一研究结果对于开发新型的非线性光学材料是十分有意义的。为了揭示它的微观机理，我们应用量子化学中的密度泛函理论计算方法对AZOPA的异构互变、电荷分布、偶极矩等性质进行了理论研究，并正在对二阶非线性极化率、三阶非线性极化率和激发态的性质进行研究。
Photorefractive materials hold great promise for optical device applications in the areas of reversible optical holography, noise-free optical signal image amplification, phase conjugate mirrors, and other optical signal processing techniques. The photorefractive effect is a light-induced change in the refractive index of a nonlinear optical material. It results from creation of an electric field induced by directional charge transport over macroscopic distances. So PR polymers attracted great interest of scientists.
Density Functional Theory is based on the self-consistent charging density. It is often the quantum mechanical method of choice because the same accuracy as high-level traditioal ab initio techniques may be attained but with a fraction of the computational time. Larger molecules can be studied with DFT.
In this article, we synthesis a new compound which can be chosen to be the electro-optic chromophore, AZOPA, and investigate its molecular structure and photorefractive properties as well when it is compounded with PVK, PBA and TNF with a certain ratio. We observe the PR effect in the absence of an applied external electric field.These results indicate that this composition have highly PR performance and makes great progress in practical applications of the PR polymer, and is promising to accelerate research on the optical device applications. Wo also introduce the Density Functional Theory and applied its major method-B3LYP to calculate the properties of AZOPA and explain the tautomerism of AZOPA.
Photorefractive materials hold great promise for optical device applications in the areas of reversible optical holography, noise-free optical signal image amplification, phase conjugate mirrors, and other optical signal processing techniques. The photorefractive effect is a light-induced change in the refractive index of a nonlinear optical material. It results from creation of an electric field induced by directional charge transport over macroscopic distances. So PR polymers attracted great interest of scientists.
Density Functional Theory is based on the self-consistent charging density. It is often the quantum mechanical method of choice because the same accuracy as high-level traditioal ab initio techniques may be attained but with a fraction of the computational time. Larger molecules can be studied with DFT.
In this article, we synthesis a new compound which can be chosen to be the electro-optic chromophore, AZOPA, and investigate its molecular structure and photorefractive properties as well when it is compounded with PVK, PBA and TNF with a certain ratio. We observe the PR effect in the absence of an applied external electric field.These results indicate that this composition have highly PR performance and makes great progress in practical applications of the PR polymer, and is promising to accelerate research on the optical device applications. Wo also introduce the Density Functional Theory and applied its major method-B3LYP to calculate the properties of AZOPA and explain the tautomerism of AZOPA.
引文
1. B.E.A.Saleh and M.Carl Teich, Ftmdamentals of Photonics, (1994)chap. 18,p729
2．宋菲君，《近代光学信息处理》，北京大学出版社
3. A.Ashkin, G. D.Boyd ect., Appl. Phys. Lett., (1966)9:72
4. F.S.Chen, L.T.LaMacchia, D.B.Fraser, Appl. Phys. Lett., (1968) 13:223
5. P.Günter, J.P.Huignard, Photorefractive Materials and Theirs Applications Ⅰ, Berlin, Springer Vedag, 1988,174-175
6. K.Sutter, J.P.Huignard, P.Günter, Solid State Commun, 1990,74(8):867-870
7. K.Sutter, P.Günter, J.Opt.Soc.Am., B1990, 7(12):2274-2768
8．袁保红、孙秀冬、姜永远等，《光折变聚合物材料的研究进展》，《物理学进展》，Vol．20，No．2，2002
9. S.Ducharme, J.C.Scott, R.J.Twieg, et al., Phys. Rev.Lett., 1991, 66 (14):1846-1849
10. M.C.J.M.Donckers, S.M.Silence, C.A.Walsh, Opt.Lett., 1993,18(13): 1044-1046
11. K.Meerhoiz, B.L.Volodin, Sandalphon, B.Kippeken and N.Peyghambarian, Nature,(1994) 371,497
12. B.L.Volodin, Sandaphon, K.Meerholz, B.Kippelen, N.V.Kukhtarev and N.Peyghambarian, Opt. Engin., (1995), 34,2213
13. W.E.Moerner, A.Grunnet-Jepsen, C.L.Thompson, M.S.Bratcher and R.J.Twieg ,SPIE, (1997)3147,84
14. F.Wang, Z.Chen, Z.Huang, Q.H.Gong, Y.Chen and H.Y.Chen Appl.
Phys.,(1998) B67,207
15. S.Bartkiewicz, A.Miniewicz ect., Appl. Opt., (1998)37,6871
16. M.A.Diaz-Garica, D.Wright, J.D.Casperson ect., Chem Mater (1999) 11, 1784
17．施磊、赵有源、闵克、汪长春，《掺杂有机给体与受体分子的向列相液晶的光折变研究》，《光学学报》，Vol．22，No．3，March，2002
18．巩永进，朱湛，郭炳南等，《光折变聚合物的研究进展》，《化学通报》，1999年第二期
19．张克从、王希敏，《非线性光学晶体材料科学》，科学出版社，1996年5月版
20. W.E.Moerner and S.M.Silence, Chem. Rev., (1994)94, 127
21．费浩生，《非线性光学》，高等教育出版社，1990年5月版
22. L.Onsager, Phys.Rev., 1988,54, 554
23. J.X.Mack, L.B.Schein and A.Peled, 1992, Appl.Phys.Rev., B65,817
24. G.C.Valley, and M.B.Klein, 1983, Opt.Eng., 22,704
25．鲍信先、李淳飞，《有机光折变材料的新进展》，《物理》
26. N.V.Kukhtarev, V.B.Markov, M.Soskin ect., 1979, Ferroelectrics, 22, 949
27．陈军，《光学位相共轭及其应用》，科学出版社，1999年11月版
28．樊美公等，《光化学基本原理与光子学材料科学》，科学出版社，2001年2月版
29. M.E.Moerner, S.M.Silence, EHache and G.C.Bjorklund, 1994, J. Opt. Soc. Am., Bll,320
30. S.Chrétien and D.R.Salahnb, Density Functional Theory, Methods, Techniques and Applications, EDP Sciences, Springer-Velag, Caneda, 2001
31. H.Thomas, Proc.Cambridge.Phil.Soc., 23 (1926) 542; E.Fermi., Z.Phys., 48 (1928) 73
32. M.Born and R.Oppenheimer, Ann.Phys., 4 (1927) 457
33. E.Sehrdinger, Ann.Phys., 79 (1926) 361
34. P.Hohenberg and W.Kohn, Phys.Rev. 136 (1964) B864
35. W.Kohn and L.J.Sham, Phys.Rev. 140 (1965) A1133
36. T.K.Woo, P.M.Margl, L.Deng, L.Cavallo and T.Ziegler, Catalysis Today, 50 (1999) 479
37. C.Alhambra, L.Wu, Z.Y.Zhang and J.Gao, J.Am.Chem.Soc., 120 (1998) 3858
38. James B. Foresman and Aeleen Frisch, Exploring Chemistry with Electronic Structure Method, Gaussian, Inc.Pittsburgh, PA. 2002
39．蒙大桥、蒋刚、刘晓亚、罗德礼、张万箱、朱正和，P u 3体系的结构与势能函数[J] ，物理学报，Vol．50，No．7(2001)：1268～1273
40. Kohn W., Beckc A.D., ParrR.G, J.Phys.Chem.[J] , 1996, 100:12974—12980
41．张广丰等，铀碳氧系统分子结构的D F T计算，原子与分子物理学报，2001，18(4)：372～376
2．宋菲君，《近代光学信息处理》，北京大学出版社
3. A.Ashkin, G. D.Boyd ect., Appl. Phys. Lett., (1966)9:72
4. F.S.Chen, L.T.LaMacchia, D.B.Fraser, Appl. Phys. Lett., (1968) 13:223
5. P.Günter, J.P.Huignard, Photorefractive Materials and Theirs Applications Ⅰ, Berlin, Springer Vedag, 1988,174-175
6. K.Sutter, J.P.Huignard, P.Günter, Solid State Commun, 1990,74(8):867-870
7. K.Sutter, P.Günter, J.Opt.Soc.Am., B1990, 7(12):2274-2768
8．袁保红、孙秀冬、姜永远等，《光折变聚合物材料的研究进展》，《物理学进展》，Vol．20，No．2，2002
9. S.Ducharme, J.C.Scott, R.J.Twieg, et al., Phys. Rev.Lett., 1991, 66 (14):1846-1849
10. M.C.J.M.Donckers, S.M.Silence, C.A.Walsh, Opt.Lett., 1993,18(13): 1044-1046
11. K.Meerhoiz, B.L.Volodin, Sandalphon, B.Kippeken and N.Peyghambarian, Nature,(1994) 371,497
12. B.L.Volodin, Sandaphon, K.Meerholz, B.Kippelen, N.V.Kukhtarev and N.Peyghambarian, Opt. Engin., (1995), 34,2213
13. W.E.Moerner, A.Grunnet-Jepsen, C.L.Thompson, M.S.Bratcher and R.J.Twieg ,SPIE, (1997)3147,84
14. F.Wang, Z.Chen, Z.Huang, Q.H.Gong, Y.Chen and H.Y.Chen Appl.
Phys.,(1998) B67,207
15. S.Bartkiewicz, A.Miniewicz ect., Appl. Opt., (1998)37,6871
16. M.A.Diaz-Garica, D.Wright, J.D.Casperson ect., Chem Mater (1999) 11, 1784
17．施磊、赵有源、闵克、汪长春，《掺杂有机给体与受体分子的向列相液晶的光折变研究》，《光学学报》，Vol．22，No．3，March，2002
18．巩永进，朱湛，郭炳南等，《光折变聚合物的研究进展》，《化学通报》，1999年第二期
19．张克从、王希敏，《非线性光学晶体材料科学》，科学出版社，1996年5月版
20. W.E.Moerner and S.M.Silence, Chem. Rev., (1994)94, 127
21．费浩生，《非线性光学》，高等教育出版社，1990年5月版
22. L.Onsager, Phys.Rev., 1988,54, 554
23. J.X.Mack, L.B.Schein and A.Peled, 1992, Appl.Phys.Rev., B65,817
24. G.C.Valley, and M.B.Klein, 1983, Opt.Eng., 22,704
25．鲍信先、李淳飞，《有机光折变材料的新进展》，《物理》
26. N.V.Kukhtarev, V.B.Markov, M.Soskin ect., 1979, Ferroelectrics, 22, 949
27．陈军，《光学位相共轭及其应用》，科学出版社，1999年11月版
28．樊美公等，《光化学基本原理与光子学材料科学》，科学出版社，2001年2月版
29. M.E.Moerner, S.M.Silence, EHache and G.C.Bjorklund, 1994, J. Opt. Soc. Am., Bll,320
30. S.Chrétien and D.R.Salahnb, Density Functional Theory, Methods, Techniques and Applications, EDP Sciences, Springer-Velag, Caneda, 2001
31. H.Thomas, Proc.Cambridge.Phil.Soc., 23 (1926) 542; E.Fermi., Z.Phys., 48 (1928) 73
32. M.Born and R.Oppenheimer, Ann.Phys., 4 (1927) 457
33. E.Sehrdinger, Ann.Phys., 79 (1926) 361
34. P.Hohenberg and W.Kohn, Phys.Rev. 136 (1964) B864
35. W.Kohn and L.J.Sham, Phys.Rev. 140 (1965) A1133
36. T.K.Woo, P.M.Margl, L.Deng, L.Cavallo and T.Ziegler, Catalysis Today, 50 (1999) 479
37. C.Alhambra, L.Wu, Z.Y.Zhang and J.Gao, J.Am.Chem.Soc., 120 (1998) 3858
38. James B. Foresman and Aeleen Frisch, Exploring Chemistry with Electronic Structure Method, Gaussian, Inc.Pittsburgh, PA. 2002
39．蒙大桥、蒋刚、刘晓亚、罗德礼、张万箱、朱正和，P u 3体系的结构与势能函数[J] ，物理学报，Vol．50，No．7(2001)：1268～1273
40. Kohn W., Beckc A.D., ParrR.G, J.Phys.Chem.[J] , 1996, 100:12974—12980
41．张广丰等，铀碳氧系统分子结构的D F T计算，原子与分子物理学报，2001，18(4)：372～376