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Journal of the Optical Society of America B

Journal of the Optical Society of America B


  • Vol. 15, Iss. 11 — Nov. 1, 1998
  • pp: 2721–2730

Quantum theory and experimental studies of absorption spectra and photoisomerization of azobenzene polymers

Thomas Garm Pedersen, P. S. Ramanujam, Per Michael Johansen, and Søren Hvilsted  »View Author Affiliations

JOSA B, Vol. 15, Issue 11, pp. 2721-2730 (1998)

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The microscopic properties of azobenzene chromophores are important for a correct description of optical storage systems based on photoinduced anisotropy in azobenzene polymers. A quantum model of these properties is presented and verified by comparison to experimental absorption spectra for <i>trans</i> and <i>cis</i> isomers of cyano methoxy azobenzene. In addition, the <i>trans</i>→<i>cis</i> quantum efficiency is measured, and hence the combined experimental and theoretical work allows one to determine the essential molecular properties, including magnitude and anisotropy of the absorption cross section and various components of the polarizability tensor for both <i>trans</i> and <i>cis</i> isomers. It is shown that the <i>trans</i> isomer is almost perfectly anisotropic, whereas the <i>cis</i> isomer is approximately isotropic in the plane containing the central C—N=N—C azobridge. The implications for models of the storage mechanism are discussed.

© 1998 Optical Society of America

OCIS Codes
(160.4890) Materials : Organic materials
(210.4810) Optical data storage : Optical storage-recording materials
(260.5130) Physical optics : Photochemistry
(300.1030) Spectroscopy : Absorption

Thomas Garm Pedersen, P. S. Ramanujam, Per Michael Johansen, and Søren Hvilsted, "Quantum theory and experimental studies of absorption spectra and photoisomerization of azobenzene polymers," J. Opt. Soc. Am. B 15, 2721-2730 (1998)

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  1. H. Rau, “Azo compounds,” in Photochromism Molecules and Systems, H. Dürr and H. Bouas-Laurent, eds. (Elsevier, Amsterdam, 1990).
  2. M. Eich, J. H. Wendorff, B. Reck, and H. Ringsdorf, “Reversible digital and holographic optical storage in polymeric liquid crystals,” Makromol. Chem. 8, 59 (1987).
  3. M. Eich and J. H. Wendorff, “Laser-induced gratings and spectroscopy in monodomains of liquid-crystalline polymers,” J. Opt. Soc. Am. B 7, 1428 (1990).
  4. K. D. Singer, J. E. Sohn, L. A. King, H. M. Gordon, H. E. Katz, and C. W. Dirk, “Second-order nonlinear-optical properties of donor- and acceptor-substituted aromatic compounds,” J. Opt. Soc. Am. B 6, 1339 (1989).
  5. Y. Shuto, “Quadratic hyperpolarizabilities of nitro-substituted pseudo-linear dye molecules with ethylenic and azo bridges,” Int. J. Quantum Chem. 58, 407 (1996).
  6. J. O. Morley, “Theoretical investigation of the electronic properties of donor-acceptor N-benzylideneanilines and related molecules,” J. Chem. Soc., 731 (1995).
  7. J. O. Morley, “Calculation of the electronic structure and nonlinear optical properties of three blue dyes,” J. Mol. Struct. 362, 235 (1996).
  8. R. Pariser and R. Parr, “A semi-empirical theory of the electronic spectra and electronic structure of complex unsaturated molecules. II,” J. Chem. Phys. 21, 466 (1953).
  9. J. A. Pople, “Electronic interaction in unsaturated hydrocarbons,” Trans. Faraday Soc. 49, 1375 (1953).
  10. J. A. Pople, “The electronic spectra of aromatic molecules. II,” Proc. Phys. Soc. London, Sec. A 68, 81 (1955).
  11. S. Hvilsted, F. Andruzzi, C. Kulinna, H. W. Siesler, and P. S. Ramanujam, “Novel side-chain liquid crystalline polyester architecture for reversible optical storage,” Macromolecules 28, 2172 (1995).
  12. T. G. Pedersen and P. M. Johansen, “Mean-field theory of photoinduced molecular reorientation in azobenzene liquid crystalline side-chain polymers,” Phys. Rev. Lett. 79, 2470 (1997).
  13. T. G. Pedersen, P. M. Johansen, N. C. R. Holme, P. S. Ramanujam, and S. Hvilsted, “Theoretical model of photoinduced anisotropy in liquid crystalline azobenzene side-chain polyesters,” J. Opt. Soc. Am. B 15, 1120 (1998).
  14. N. C. R. Holme, P. S. Ramanujam, and S. Hvilsted, “Photoinduced anisotropy measurements in liquid-crystalline side-chain polyesters,” Appl. Opt. 35, 4622 (1996).
  15. D. L. Beveridge and H. H. Jaffé, “The electronic structure and spectra of cis- and trans-azobenzene,” J. Am. Chem. Soc. 88, 1948 (1966).
  16. M. Traetteberg, I. Hilmo, and K. Hagen, “A gas electron diffraction study of the molecular structure of trans-azobenzene,” J. Mol. Struct. 39, 231 (1977).
  17. S. Monti, G. Orlandi, and P. Palmeri, “Features of the photochemically active state surfaces of azobenzene,” Chem. Phys. 71, 87 (1982).
  18. J. Griffiths, “Practical properties of colour prediction of organic dye molecules,” Dyes Pigm. 3, 211 (1982).
  19. L. Salem, The Molecular Orbital Theory of Conjugated Systems (Benjamin, New York, 1966).
  20. M. Weissbluth, Photon-Atom Interactions (Academic, San Diego, Calif., 1989).
  21. Y. R. Shen, The Principles of Nonlinear Optics (Wiley, New York, 1984).
  22. D. Grasso, S. Millefiori, and S. Fasone, “Solvent effect on the absorption spectra of substituted azobenzenes,” Spectrochim. Acta A 31, 187 (1975).
  23. G. Zimmerman, L. Chow, and U. Paik, “The photochemical isomerization of azobenzene,” J. Am. Chem. Soc. 80, 3528 (1958).
  24. E. Fischer, “The calculation of photostationary states in systems A↔B when only A is known,” J. Phys. Chem. 71, 3704 (1967).
  25. I. K. Lednev, T. Q. Ye, R. E. Hester, and J. N. Moore, “Femtosecond time-resolved UV–visible absorption spectroscopy of trans-azobenzene in solution,” J. Phys. Chem. 100, 13338 (1996).
  26. Z. Sekkat and M. Dumont, “Photoinduced orientation of azo dyes in polymeric films. Characterization of molecular angular mobility,” Synth. Met. 54, 373 (1993).
  27. M. Dumont, G. Froc, and S. Hosotte, “Alignment and orientation of chromophores by optical pumping,” Nonlinear Opt. 9, 327 (1995).
  28. P. S. Ramanujam, S. Hvilsted, I. Zebger, and H. W. Siesler, “On the explanation of the biphotonic processes in polyesters containing azobenzene in the side chain,” Macromol. Rapid Commun. 16, 455 (1995).
  29. K. Ohno, “Some remarks on the Pariser–Parr–Pople method,” Theor. Chim. Acta 2, 219 (1964).
  30. I. D. L. Albert, S. Ramasesha, and P. K. Das, “Properties of some low-lying electronic states in polymethineimines and poly(2, 3-diazabutadienes),” Phys. Rev. B 43, 7013 (1991).
  31. A. Takahashi and S. Mukamel, “Anharmonic oscillator modelling of nonlinear susceptibilities and its applications to conjugated polymers,” J. Chem. Phys. 100, 2366 (1994).

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