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Journal of the Optical Society of America B

Journal of the Optical Society of America B

| OPTICAL PHYSICS

  • Editor: Henry M. Van Driel
  • Vol. 24, Iss. 1 — Jan. 1, 2007
  • pp: 56–66

Molecular structure—two-photon absorption property relations in polymethine dyes

Jie Fu, Lazaro A. Padilha, David J. Hagan, Eric W. Van Stryland, Olga V. Przhonska, Mikhail V. Bondar, Yuriy L. Slominsky, and Alexei D. Kachkovski  »View Author Affiliations


JOSA B, Vol. 24, Issue 1, pp. 56-66 (2007)
http://dx.doi.org/10.1364/JOSAB.24.000056


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Abstract

We performed a comprehensive experimental investigation of two-photon absorption (2PA) spectra of a series of 12 symmetrical and asymmetrical cationic polymethine dyes, including complete one-and two-photon excitation anisotropy measurements. Quantum-chemical calculations were performed with the goal of understanding the nature of 2PA bands and of uncovering structure-property relations. We found that there are 2PA bands in the spectral region between the first absorption band and that for twice its energy. A weakly allowed 2PA band within the short-wavelength shoulder of the first absorption band was observed owing to the effects of vibrational and charge distribution symmetry breaking. The nature of the strongest 2PA band is connected to the electron transition from the molecular orbital localized at the benzene rings of the terminal groups to the lowest unoccupied molecular orbital (LUMO). Structure-property relations revealed that the 2PA cross section tends to be enhanced by either an increase in the length of the polymethine chromophore or an increase in the donor strengths in the terminal groups.

© 2006 Optical Society of America

OCIS Codes
(190.4180) Nonlinear optics : Multiphoton processes
(190.4710) Nonlinear optics : Optical nonlinearities in organic materials

ToC Category:
Nonlinear Optics

History
Original Manuscript: May 30, 2006
Manuscript Accepted: August 29, 2006

Virtual Issues
Vol. 2, Iss. 2 Virtual Journal for Biomedical Optics

Citation
Jie Fu, Lazaro A. Padilha, David J. Hagan, Eric W. Van Stryland, Olga V. Przhonska, Mikhail V. Bondar, Yuriy L. Slominsky, and Alexei D. Kachkovski, "Molecular structure—two-photon absorption property relations in polymethine dyes," J. Opt. Soc. Am. B 24, 56-66 (2007)
http://www.opticsinfobase.org/josab/abstract.cfm?URI=josab-24-1-56


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References

  1. S. R. Marder, "Organic nonlinear optical materials: where we have been and where we are going," Chem. Commun. (Cambridge)131-134 (2006).
  2. M. Albota, D. Beljonne, J. L. Bredas, J. E. Ehrlich, J.-Y. Fu, A. A. Heikal, S. Hess, T. Kogej, M. D. Levin, S. R. Marder, D. McCord-Maughon, J. W. Perry, H. Rockel, M. Rumi, G. Subramaniam, W. W. Webb, X.-L. Wu, and C. Xu, "Design of organic molecules with large two-photon absorption cross sections," Science 281, 1653-1656 (1998). [CrossRef] [PubMed]
  3. T. Kogej, D. Beljonne, F. Meyers, J. W. Perry, S. R. Marder, and J. L. Bredas, "Mechanisms for enhancement of two-photon absorption in donor-acceptor conjugated chromophores," Chem. Phys. Lett. 298, 1-3 (1998). [CrossRef]
  4. M. Rumi, J. E. Ehrlich, A. A. Heikal, J. W. Perry, S. Barlow, Z. Hu, D. McCord-Maughon, T. C. Parker, H. Rocker, S. Thayumanavan, S. R. Marder, D. Beljonne, and J. L. Bredas, "Structure-property relationships for two-photon absorbing chromophores: bis-donor diphenylpolyene and bis(styryl)benzene derivatives," J. Am. Chem. Soc. 122, 9500-9510 (2000). [CrossRef]
  5. G. S. He, T.-C. Lin, J. Dai, P. N. Prasad, R. Kannan, A. G. Dombroskie, R. A. Vaia, and L.-S. Tan, "Degenerate two-photon-absorption spectral studies of highly two-photon active organic chromophores," J. Chem. Phys. 120, 5275-5284 (2004). [CrossRef] [PubMed]
  6. C.-K. Wang, P. Macak, Yi Luo, and H. Agren, "Effects of π centers and symmetry on two-photon absorption cross sections of organic chromophores," J. Chem. Phys. 114, 9813-9820 (2001). [CrossRef]
  7. E. Zojer, D. Beljonne, T. Kogej, H. Vogel, S. R. Marder, J. W. Perry, and J. L. Bredas, "Tuning the two-photon absorption response of quadrupolar organic molecules," J. Chem. Phys. 116, 3646-3658 (2002). [CrossRef]
  8. E. Zojer, D. Beljonne, P. Pacher, and J. L. Bredas, "Two-photon absorption in quadrupolar π-conjugated molecules: influence of the nature of the conjugated bridge and the donor-acceptor separation," Chem.-Eur. J. 10, 2668-2680 (2004). [CrossRef] [PubMed]
  9. R. S. Lepkowicz, O. V. Przhonska, J. M. Hales, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Excited-state absorption dynamics in polymethine dyes detected by polarization-resolved pump-probe measurements," Chem. Phys. 286, 277-291 (2003). [CrossRef]
  10. J. M. Hales, D. J. Hagan, E. W. Van Stryland, K. J. Schafer, A. R. Morales, K. D. Belfield, P. Pacher, O. Kwon, E. Zojer, and J. L. Bredas, "Resonant enhancement of two-photon absorption in substituted fluorene molecules," J. Chem. Phys. 121, 3152-3160 (2004). [CrossRef] [PubMed]
  11. M. Hamer, The Cyanine Dyes and Related Compounds (Interscience, 1964).
  12. J. R. Lakowicz, Principles of Fluorescence Spectroscopy (Kluwer Academic/Plenum, 1999).
  13. M. Sheik-Bahae, A. A. Said, and E. W. Van Stryland, "High-sensitivity, single-beam n2 measurements," Opt. Lett. 14, 955-957 (1989). [CrossRef] [PubMed]
  14. C. Xu and W. W. Webb, "Measurement of two-photon excitation cross sections of molecular fluorophores with data from 690to1050 nm," J. Opt. Soc. Am. B 13, 481-491 (1996). [CrossRef]
  15. M. Sheik-Bahae, A. A. Said, T.-H. Wei, D. R. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Sel. Top. Quantum Electron. 26, 760-769 (1990). [CrossRef]
  16. M. Fisher and J. Georges, "Fluorescence quantum yield of Rhodamine 6G in ethanol as a function of concentration using thermal lens spectrometry," Chin. Phys. Lasers 260, 115-118 (1996). [CrossRef]
  17. J. Fu, O. V. Przhonska, L. A. Padilha, D. J. Hagan, E. W. Van Stryland, K. D. Belfield, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Two-photon anisotropy: analytical description and molecular modeling for symmetrical and asymmetrical organic dyes," Chem. Phys. 321, 257-268 (2006). [CrossRef]
  18. M. J. S. Dewar, The Molecular Orbital Theory of Organic Chemistry (McGraw-Hill, 1969).
  19. J. S. Craw, J. R. Reimers, G. B. Bacskay, A. T. Wong, and N. S. Hush, "Solitons in finite- and infinite-length negative-defect trans-polyacetylene and the corresponding Brooker (polymethinecyanine) cations," Chem. Phys. 167, 77-99 (1992). [CrossRef]
  20. J. Fu, O. V. Przhonska, L. A. Padilha, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Experimental and theoretical approaches to understanding two-photon absorption spectra in polymethine and squaraine molecules," J. Opt. Soc. Am. B 24, 67-76 (2007). [CrossRef]
  21. R. S. Lepkowicz, O. V. Przhonska, J. M. Hales, J. Fu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Nature of the electronic transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004). [CrossRef]
  22. K. Kamada, K. Ohta, Y. Iwase, and K. Kondo, "Two-photon absorption properties of symmetric substituted diacetylene: drastic enhancement of the cross section near the one-photon absorption peak," Chem. Phys. Lett. 372, 386-393 (2003). [CrossRef]
  23. D. Scherer, R. Dorfler, A. Feldner, T. Vogtmann, M. Schwoerer, U. Lawrentz, W. Grahn, and C. Lambert, "Two-photon states in squaraine monomers and oligomers," Chem. Phys. 279, 179-207 (2002). [CrossRef]

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