光学

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えみいさし
5 years ago
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1 Control of Refractive Indices of Optical Polymers: Theoretical Prediction and Molecular Design Method Shinji ANDO The fundamental theory and a method to predict the refractive indices and dispersions of organic molecules and optical polymers were outlined. The e ects of substituents exerting on the refractive index of organic molecules are quantified from an analysis of the empirical molecular refractions and molar volumes of mono-substituted benzenes. When density of an organic molecule is known, its refractive index and the wavelength dispersion can be predicted with a high accuracy based on the Lorentz-Lorenz formula because the wavelength dispersion of molecular polarizabilities are well reproduced by the density functional theory DFT. A series of thermally stable sulfur-containing polyimides with high refractive indices and low dispersion were newly designed and synthesized based on the above method. It was confirmed that DFT calculation is a useful tool to design new optical polymers with controlled refractive indices and dispersions. Key words: refractive index, dispersion, polymer, DFT calculation, high refractive index polymer l nm n 1.8 D n n C V n C/V a n a L L 2 n 1 4π 4π ρn N 2 α A α n M R V 0 φ E4 5 sando@polymer.titech.ac.jp 298 2

2 1 6 7 R H N C N C C N C C N C 6 H N C 10 H N O C O N OO H N O, C O N F 0.95 N Cl N Br N I NC N S C S 7.97 N S S H 7.69 NO 2 S S S 8.11 NO NO NO 2 R φ n 2 1 φ N r N A M V 0 M/r r R a a 2 3 n a K K 8 n n nm n589 1 ν 3 n486 n656 n n n 1 2. L L R /V 0 V int V 0 /N A a /V int 1 n R /V 0 a /V int V vdw a V vdw V int K p R /V 0 a /V vdw S Br, I K p 299 3

3 SC 6 H 5 COC 6 H 5 OC 6 H 5 C 6 H 5 NH 2 NO 2 OH CN OCH 3 IBr Cl SC 6 H 5 F 2 a R /V 0 b R /V K p l 589 nm R /V R 1 V 0 M r TD-DFT PI l nm l nm n a Gaussian 09 Rev.C-01 functional a 2 V int L L DFT CAM B3LYP 6 31G d G 2d,p n 3

4 3 5 n n 4ab DFT 500 nm l , 589, 656 nm a l L L 589 nm n 589 n 4 Br DFT n n n DFT n 589 n 5 n DFT 301 5

5 R R' Bicerano PMMA PSt PC n DFT 6 n n PSt PC n S SO DFT S c PI PI PI s-bpda 7 APTT PI l nm n l 8 n S c SO 2 BADPS

6 n VIS n b n PI PI n 1.75 DFT 9 a b n CT S c n CHDA, CBDA CT n 1.72 PI n l n D/l 2 n D 9 a PI n D PI D ODPA mdpsda PI PI CBDA CHDA 3SDEA s-bpda PI l 633, 845, 1324 nm J. A. Dean: Lange s Handbook of Chemistry, 15th ed. McGraw- Hill, M. Fox: Optical Properties of Solids Oxford Univ. Press, M. Schmidt, A. Brodin, P. Jacobsson and F. H. J. Maurer: J. Chem. Phys., G. L. Slonimskii, A. A. Askadskii and A. I. Kitaigotodskii: Polym. Sci. USSR, A A. Javadi, A. Shockravi, A. Rafieimanesh, A. M. Malek and S. Ando: Polym. Int., S. Ando: J. Photopolym. Sci. Technol., S. Ando, T. Fujigaya and M. Ueda: J. Photopolym. Sci. Technol., S. Ando and M. Ueda: J. Photopolym. Sci. Technol., Y. Terui and S. Ando: J. Polym. Sci. Part B: Polym. Phys., S. Ando: in preparation. 17 J. Bicerano: Prediction of Polymer Properties CRC Press, J.-G. Liu, Y. Nakamura, Y. Suzuki, Y. Shibasaki, S. Ando and M. Ueda: Macromolecules, J.-G. Liu, Y. Nakamura, Y. Shibasaki, S. Ando and M. Ueda: J. Polym. Sci. Part A: Polym. Chem., J.-G. Liu, Y. Nakamura, Y. Suzuki, Y. Shibasaki, S. Ando and M. Ueda: Macromolecules, J-G. Liu, Y. Nakamura, T. Ogura, Y. Shibasaki, S. Ando and M. Ueda: Chem. Mater., R. Okutsu, S. Ando and M. Ueda: Chem. Mater., R. Okutsu, Y. Suzuki, S. Ando and M. Ueda: Macromolecules, N.-H. You, Y. Suzuki, D. Yorifuji, S. Ando and M. Ueda: Macromolecules, C. A. Terraza, J.-G. Liu, Y. Nakamura, Y. Shibasaki, S. Ando and M. Ueda: J. Polym. Sci. Part A: Polym. Chem., N.-H. You, Y. Suzuki, T. Higashihara, S. Ando and M. Ueda: Polymer, Y. Suzuki, T. Higashihara S. Ando and M. Ueda: Eur. Polym. J.,

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