Abstract

The linear and nonlinear optical properties of a series of polymethine molecules are investigated to study the effects of molecular structure and the host environment on overall nonlinear absorption performance. The linear characterization includes measuring the solvatochromic shifts between absorption and fluorescence peaks and studying the excited-state orientational diffusion kinetics. The nonlinear characterization involves measuring the excited-state absorption spectra with a femtosecond white-light-continuum pump–probe technique and performing Z scans and nonlinear transmission measurements from the picosecond to the nanosecond time regimes. The results of these experiments allow us to develop an energy-level structure for the polymethines, which accurately predicts nonlinear absorption properties from the picosecond to the nanosecond time regimes. From this model we are able to identify the key molecular parameters for improved nonlinear absorption.

© 2005 Optical Society of America

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    [CrossRef]
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    [CrossRef]
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    [CrossRef] [PubMed]
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    [CrossRef]
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  32. D. I. Kovsh, D. J. Hagan, and E. W. Van Stryland, "Numerical modeling of thermal refraction in liquids in the transient regime," Opt. Express 4, 315-327 (1999).
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2004 (2)

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

2003 (1)

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]

2002 (2)

D. A. Oulianov, A. S. Dvornikov, and P. M. Rentzepis, "Optical limiting and picosecond relaxation of carbocyanines upper electronic states," Opt. Commun. 205, 427-436 (2002).
[CrossRef]

R. S. Lepkowicz, A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Picosecond optical limiting in reverse saturable absorbers: a theoretical and experimental study," J. Opt. Soc. Am. B 19, 94-101 (2002).
[CrossRef]

2001 (2)

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

2000 (3)

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Analytical approach to dynamics of reverse saturable absorbers," J. Opt. Soc. Am. B 17, 1884-1893 (2000).
[CrossRef]

J. Robertson, P. Milsom, J. Duignan, and G. Bourhill, "Spatial redistribution of energy in a nanosecond laser pulse by an organic optical limiter," Opt. Lett. 25, 1258-1260 (2000).
[CrossRef]

1999 (3)

D. I. Kovsh, D. J. Hagan, and E. W. Van Stryland, "Numerical modeling of thermal refraction in liquids in the transient regime," Opt. Express 4, 315-327 (1999).
[CrossRef] [PubMed]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
[CrossRef]

1998 (1)

1997 (3)

1996 (1)

S. Hughes and B. Wherrett, "Multilevel rate-equation analysis to explain the recent observations of limitations to optical limiting dyes," Phys. Rev. A 54, 3546-3552 (1996).
[CrossRef] [PubMed]

1995 (2)

S. N. R. Swatton, K. R. Welford, S. J. Till, and J. R. Sambles, "Nonlinear absorption of a carbocyanine dye 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide using a z-scan technique," Appl. Phys. Lett. 66, 1868-1870 (1995).
[CrossRef]

M. Levitus, R. M. Negri, and P. F. Aramdenia, "Rotational relaxation of carbocyanines. Comparative study with the isomerization dynamics," J. Phys. Chem. 99, 14231-14239 (1995).
[CrossRef]

1993 (1)

L. W. Tutt and T. F. Boggess, "A review of optical limiting mechanisms and devices using organics, fullerenes, semiconductors and other materials," Prog. Quantum Electron. 17, 299-338 (1993).
[CrossRef]

1990 (2)

G. B. Dutt, S. Doraiswamy, N. Periasamy, and B. Venkataraman, "Rotational reorientation dynamics of polar dye molecular probes by picosecond laser spectroscopic technique," J. Chem. Phys. 93, 8498-8513 (1990).
[CrossRef]

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Quantum Electron. 26, 760-769 (1990).
[CrossRef]

1988 (1)

F. Momicchioli, I. Baraldi, and G. Berthier, "Theoretical study of trans-cis photoisomerism in polymethine cyanines," Chem. Phys. 123, 103-112 (1988).
[CrossRef]

1983 (1)

1974 (1)

C. Hu and R. Zwanzig, "Rotational friction coefficients for spheroids with the slipping boundary condition," J. Chem. Phys. 60, 4354-4357 (1974).
[CrossRef]

1934 (1)

F. Perrin, "Mouvement brownien d'un ellipsoide (I). Dispersion dielectrique pour des molecules ellipsoidales," J. Phys. Radium 5, 497-511 (1934).
[CrossRef]

Aramdenia, P. F.

M. Levitus, R. M. Negri, and P. F. Aramdenia, "Rotational relaxation of carbocyanines. Comparative study with the isomerization dynamics," J. Phys. Chem. 99, 14231-14239 (1995).
[CrossRef]

Baraldi, I.

F. Momicchioli, I. Baraldi, and G. Berthier, "Theoretical study of trans-cis photoisomerism in polymethine cyanines," Chem. Phys. 123, 103-112 (1988).
[CrossRef]

Berthier, G.

F. Momicchioli, I. Baraldi, and G. Berthier, "Theoretical study of trans-cis photoisomerism in polymethine cyanines," Chem. Phys. 123, 103-112 (1988).
[CrossRef]

Boggess, T. F.

L. W. Tutt and T. F. Boggess, "A review of optical limiting mechanisms and devices using organics, fullerenes, semiconductors and other materials," Prog. Quantum Electron. 17, 299-338 (1993).
[CrossRef]

Bondar, M. V.

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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]

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

O. V. Przhonska, J. H. Lim, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Y. L. Slominsky, "Nonlinear light absorption of polymethine dyes in liquid and solid media," J. Opt. Soc. Am. B 15, 802-809 (1998).
[CrossRef]

Bourhill, G.

Brochard, P.

Cabanel, R.

Cirloganu, C. M.

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

Deng, X.

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
[CrossRef]

Dogariu, A.

Doraiswamy, S.

G. B. Dutt, S. Doraiswamy, N. Periasamy, and B. Venkataraman, "Rotational reorientation dynamics of polar dye molecular probes by picosecond laser spectroscopic technique," J. Chem. Phys. 93, 8498-8513 (1990).
[CrossRef]

Duignan, J.

Dutt, G. B.

G. B. Dutt, S. Doraiswamy, N. Periasamy, and B. Venkataraman, "Rotational reorientation dynamics of polar dye molecular probes by picosecond laser spectroscopic technique," J. Chem. Phys. 93, 8498-8513 (1990).
[CrossRef]

Dvornikov, A. S.

D. A. Oulianov, A. S. Dvornikov, and P. M. Rentzepis, "Optical limiting and picosecond relaxation of carbocyanines upper electronic states," Opt. Commun. 205, 427-436 (2002).
[CrossRef]

Fleming, G. R.

G. R. Fleming, Chemical Applications of Ultrafast Spectroscopy (Oxford U. Press, 1986).

Fork, R. L.

Fu, J.

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

Grolier-Mazza, V.

Hagan, D. J.

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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]

R. S. Lepkowicz, A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Picosecond optical limiting in reverse saturable absorbers: a theoretical and experimental study," J. Opt. Soc. Am. B 19, 94-101 (2002).
[CrossRef]

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Analytical approach to dynamics of reverse saturable absorbers," J. Opt. Soc. Am. B 17, 1884-1893 (2000).
[CrossRef]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

D. I. Kovsh, D. J. Hagan, and E. W. Van Stryland, "Numerical modeling of thermal refraction in liquids in the transient regime," Opt. Express 4, 315-327 (1999).
[CrossRef] [PubMed]

O. V. Przhonska, J. H. Lim, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Y. L. Slominsky, "Nonlinear light absorption of polymethine dyes in liquid and solid media," J. Opt. Soc. Am. B 15, 802-809 (1998).
[CrossRef]

T. Xia, D. J. Hagan, A. Dogariu, A. Said, and E. W. Van Stryland, "Optimization of optical limiting devices based on excited-state absorption," Appl. Opt. 36, 4110-4122 (1997).
[CrossRef] [PubMed]

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Quantum Electron. 26, 760-769 (1990).
[CrossRef]

E. W. Van Stryland, D. J. Hagan, T. Xia, and A. A. Said, "Application of nonlinear optics to passive optical limiting," in Nonlinear Optics of Organic Molecules and Polymers, H.S.Nalwa and S.Miyata, eds. (CRC Press, 1997), pp. 841-860.

Hales, J. M.

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

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]

Hamer, M.

M. Hamer, The Cyanine Dyes and Related Compounds (Interscience, 1964).

Hirlimann, C.

Hu, C.

C. Hu and R. Zwanzig, "Rotational friction coefficients for spheroids with the slipping boundary condition," J. Chem. Phys. 60, 4354-4357 (1974).
[CrossRef]

Hughes, S.

S. Hughes and B. Wherrett, "Multilevel rate-equation analysis to explain the recent observations of limitations to optical limiting dyes," Phys. Rev. A 54, 3546-3552 (1996).
[CrossRef] [PubMed]

Hunt, P.

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

Ischenko, A. A.

A. I. Tolmachev, Yu. L. Slominsky, and A. A. Ischenko, "New cyanine dyes absorbing in the NIR region," in Near-Infrared Dyes for High Technology Applications, S.Daehne, U.Resh-Genger, and O.S.Wolfbeis, eds., Vol. 52 of NATO Advanced Study Institute Series (Kluger Academic, 1998), pp. 385-415.
[CrossRef]

Kachkovski, A. D.

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

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]

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

Khodja, S.

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

Kobyakov, A.

Kovsh, D. I.

Lakowicz, J. R.

J. R. Lakowicz, Principles of Fluorescence Spectroscopy, 2nd ed. (Kluwer Academic/Plenum, 1999).
[CrossRef]

Lepkowicz, R.

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

Lepkowicz, R. S.

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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]

R. S. Lepkowicz, A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Picosecond optical limiting in reverse saturable absorbers: a theoretical and experimental study," J. Opt. Soc. Am. B 19, 94-101 (2002).
[CrossRef]

Levitus, M.

M. Levitus, R. M. Negri, and P. F. Aramdenia, "Rotational relaxation of carbocyanines. Comparative study with the isomerization dynamics," J. Phys. Chem. 99, 14231-14239 (1995).
[CrossRef]

Li, C.

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
[CrossRef]

Lim, J. H.

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

O. V. Przhonska, J. H. Lim, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Y. L. Slominsky, "Nonlinear light absorption of polymethine dyes in liquid and solid media," J. Opt. Soc. Am. B 15, 802-809 (1998).
[CrossRef]

Liu, S.

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
[CrossRef]

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M. Maroncelli, "Continuum estimates of rotational dielectric friction and polar solvation," J. Chem. Phys. 106, 1545-1555 (1997).
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Mayboroda, E. I.

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

Milsom, P.

Momicchioli, F.

F. Momicchioli, I. Baraldi, and G. Berthier, "Theoretical study of trans-cis photoisomerism in polymethine cyanines," Chem. Phys. 123, 103-112 (1988).
[CrossRef]

Negres, R. A.

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

Negri, R. M.

M. Levitus, R. M. Negri, and P. F. Aramdenia, "Rotational relaxation of carbocyanines. Comparative study with the isomerization dynamics," J. Phys. Chem. 99, 14231-14239 (1995).
[CrossRef]

Novikov, E.

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

Olivucci, M.

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

Oulianov, D. A.

D. A. Oulianov, A. S. Dvornikov, and P. M. Rentzepis, "Optical limiting and picosecond relaxation of carbocyanines upper electronic states," Opt. Commun. 205, 427-436 (2002).
[CrossRef]

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G. B. Dutt, S. Doraiswamy, N. Periasamy, and B. Venkataraman, "Rotational reorientation dynamics of polar dye molecular probes by picosecond laser spectroscopic technique," J. Chem. Phys. 93, 8498-8513 (1990).
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Przhonska, O. V.

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

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]

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

O. V. Przhonska, J. H. Lim, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Y. L. Slominsky, "Nonlinear light absorption of polymethine dyes in liquid and solid media," J. Opt. Soc. Am. B 15, 802-809 (1998).
[CrossRef]

Rentzepis, P. M.

D. A. Oulianov, A. S. Dvornikov, and P. M. Rentzepis, "Optical limiting and picosecond relaxation of carbocyanines upper electronic states," Opt. Commun. 205, 427-436 (2002).
[CrossRef]

Robb, M. A.

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

Robertson, J.

Ross, T. S.

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

Said, A.

Said, A. A.

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Quantum Electron. 26, 760-769 (1990).
[CrossRef]

E. W. Van Stryland, D. J. Hagan, T. Xia, and A. A. Said, "Application of nonlinear optics to passive optical limiting," in Nonlinear Optics of Organic Molecules and Polymers, H.S.Nalwa and S.Miyata, eds. (CRC Press, 1997), pp. 841-860.

Sambles, J. R.

S. N. R. Swatton, K. R. Welford, S. J. Till, and J. R. Sambles, "Nonlinear absorption of a carbocyanine dye 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide using a z-scan technique," Appl. Phys. Lett. 66, 1868-1870 (1995).
[CrossRef]

Sanchez-Galvez, A.

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

Schlegel, H. B.

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

Shank, C. V.

Sheik-Bahae, M.

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Quantum Electron. 26, 760-769 (1990).
[CrossRef]

Slominsky, Y. L.

Slominsky, Yu. L.

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

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]

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

A. I. Tolmachev, Yu. L. Slominsky, and A. A. Ischenko, "New cyanine dyes absorbing in the NIR region," in Near-Infrared Dyes for High Technology Applications, S.Daehne, U.Resh-Genger, and O.S.Wolfbeis, eds., Vol. 52 of NATO Advanced Study Institute Series (Kluger Academic, 1998), pp. 385-415.
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Song, Y.

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
[CrossRef]

Swatton, S. N.

S. N. R. Swatton, K. R. Welford, S. J. Till, and J. R. Sambles, "Nonlinear absorption of a carbocyanine dye 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide using a z-scan technique," Appl. Phys. Lett. 66, 1868-1870 (1995).
[CrossRef]

Till, S. J.

S. N. R. Swatton, K. R. Welford, S. J. Till, and J. R. Sambles, "Nonlinear absorption of a carbocyanine dye 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide using a z-scan technique," Appl. Phys. Lett. 66, 1868-1870 (1995).
[CrossRef]

Tolmachev, A. I.

A. I. Tolmachev, Yu. L. Slominsky, and A. A. Ischenko, "New cyanine dyes absorbing in the NIR region," in Near-Infrared Dyes for High Technology Applications, S.Daehne, U.Resh-Genger, and O.S.Wolfbeis, eds., Vol. 52 of NATO Advanced Study Institute Series (Kluger Academic, 1998), pp. 385-415.
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Tutt, L. W.

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R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

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]

R. S. Lepkowicz, A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Picosecond optical limiting in reverse saturable absorbers: a theoretical and experimental study," J. Opt. Soc. Am. B 19, 94-101 (2002).
[CrossRef]

R. A. Negres, O. V. Przhonska, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "The nature of excited-state absorption in polymethine and squarylium molecules," IEEE J. Sel. Top. Quantum Electron. 7, 849-863 (2001).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

A. Kobyakov, D. J. Hagan, and E. W. Van Stryland, "Analytical approach to dynamics of reverse saturable absorbers," J. Opt. Soc. Am. B 17, 1884-1893 (2000).
[CrossRef]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

D. I. Kovsh, D. J. Hagan, and E. W. Van Stryland, "Numerical modeling of thermal refraction in liquids in the transient regime," Opt. Express 4, 315-327 (1999).
[CrossRef] [PubMed]

O. V. Przhonska, J. H. Lim, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Y. L. Slominsky, "Nonlinear light absorption of polymethine dyes in liquid and solid media," J. Opt. Soc. Am. B 15, 802-809 (1998).
[CrossRef]

T. Xia, D. J. Hagan, A. Dogariu, A. Said, and E. W. Van Stryland, "Optimization of optical limiting devices based on excited-state absorption," Appl. Opt. 36, 4110-4122 (1997).
[CrossRef] [PubMed]

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Quantum Electron. 26, 760-769 (1990).
[CrossRef]

E. W. Van Stryland, D. J. Hagan, T. Xia, and A. A. Said, "Application of nonlinear optics to passive optical limiting," in Nonlinear Optics of Organic Molecules and Polymers, H.S.Nalwa and S.Miyata, eds. (CRC Press, 1997), pp. 841-860.

Venkataraman, B.

G. B. Dutt, S. Doraiswamy, N. Periasamy, and B. Venkataraman, "Rotational reorientation dynamics of polar dye molecular probes by picosecond laser spectroscopic technique," J. Chem. Phys. 93, 8498-8513 (1990).
[CrossRef]

Vreven, T.

A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, and H. B. Schlegel, "Ultrafast radiationless deactivation of organic dyes: evidence for a two-state two-mode pathway in polymethine cyanines," J. Am. Chem. Soc. 122, 2911-2924 (2000).
[CrossRef]

Wang, Y.

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
[CrossRef]

Wei, T. H.

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, "Sensitive measurement of optical nonlinearities using a single beam," IEEE J. Quantum Electron. 26, 760-769 (1990).
[CrossRef]

Welford, K. R.

S. N. R. Swatton, K. R. Welford, S. J. Till, and J. R. Sambles, "Nonlinear absorption of a carbocyanine dye 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide using a z-scan technique," Appl. Phys. Lett. 66, 1868-1870 (1995).
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T. Xia, D. J. Hagan, A. Dogariu, A. Said, and E. W. Van Stryland, "Optimization of optical limiting devices based on excited-state absorption," Appl. Opt. 36, 4110-4122 (1997).
[CrossRef] [PubMed]

E. W. Van Stryland, D. J. Hagan, T. Xia, and A. A. Said, "Application of nonlinear optics to passive optical limiting," in Nonlinear Optics of Organic Molecules and Polymers, H.S.Nalwa and S.Miyata, eds. (CRC Press, 1997), pp. 841-860.

Yang, S.

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

Yen, R.

Zhang, X.

X. Deng, X. Zhang, Y. Wang, Y. Song, S. Liu, and C. Li, "Intensity threshold in the conversion from reverse saturable absorption to saturable absorption and its application in optical limiting," Opt. Commun. 168, 207-212 (1999).
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Appl. Opt. (1)

Appl. Phys. Lett. (1)

S. N. R. Swatton, K. R. Welford, S. J. Till, and J. R. Sambles, "Nonlinear absorption of a carbocyanine dye 1,1',3,3,3',3'-hexamethylindotricarbocyanine iodide using a z-scan technique," Appl. Phys. Lett. 66, 1868-1870 (1995).
[CrossRef]

Chem. Phys. (6)

R. S. Lepkowicz, O. V. Przhonska, C. M. Cirloganu, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, A. D. Kachkovski, and E. I. Mayboroda, "Absorption anisotropy studies of polymethine dyes," Chem. Phys. 306, 171-183 (2004).
[CrossRef]

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 electron transitions in thiacarbocyanines with a long polymethine chain," Chem. Phys. 305, 259-270 (2004).
[CrossRef]

O. V. Przhonska, D. J. Hagan, E. Novikov, R. Lepkowicz, E. W. Van Stryland, M. V. Bondar, Yu. L. Slominsky, and A. D. Kachkovski, "Picosecond absorption anisotropy of polymethine and squarylium dyes in liquid and polymeric media," Chem. Phys. 273, 235-248 (2001).
[CrossRef]

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]

J. H. Lim, O. V. Przhonska, S. Khodja, S. Yang, T. S. Ross, D. J. Hagan, E. W. Van Stryland, M. V. Bondar, and Yu. L. Slominsky, "Polymethine and squarylium molecules with large excited-state absorption," Chem. Phys. 245, 79-97 (1999).
[CrossRef]

F. Momicchioli, I. Baraldi, and G. Berthier, "Theoretical study of trans-cis photoisomerism in polymethine cyanines," Chem. Phys. 123, 103-112 (1988).
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IEEE J. Quantum Electron. (1)

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Figures (18)

Fig. 1
Fig. 1

Linear absorption spectrum in ethanol: (a) PD 2350, (b) PD 2410, (c) PD 3428, (d) PD 1952, (e) PD 824, and (f) PD 1659.

Fig. 2
Fig. 2

Molecular structures.

Fig. 3
Fig. 3

(a) Three-level energy manifold schematic of an excited-state absorber; S 0 is the ground state, and S 1 and S 2 are the excited singlet states. (b) Schematic diagram of the four-level model of RSA.

Fig. 4
Fig. 4

Typical picosecond Z-scan results for (a) PD 824 in PC at fluences of 1.1 × 10 3 J cm 2 (circles), 2.2 × 10 3 J cm 2 (triangles), and 4.4 × 10 3 J cm 2 (squares) and fitting parameters of σ 10 = 7.8 × 10 18 cm 2 , σ 12 = 3.0 × 10 16 cm 2 , and τ 10 = 0.4 ns . (b) PD 1952 in ethanol at fluences of 2.9 × 10 3 J cm 2 (circles), 5.7 × 10 3 J cm 2 (triangles), and 9.8 × 10 3 J cm 2 (squares) and fitting parameters of σ 10 = 2.2 × 10 18 cm 2 , σ 12 = 2.8 × 10 16 cm 2 , and τ 10 = 1.3 ns .

Fig. 5
Fig. 5

Nonlinear transmission curve of PD 1952 in ethanol at different repetition rates: (1) 10 Hz, (2) 5 Hz, and (3) 1 Hz to demonstrate photodegradation effect.

Fig. 6
Fig. 6

Picosecond nonlinear transmission curves with fits using the four-level model shown in Fig. 3b: (a) PD 2350 in pentanol, (b) PD 1952 in PC, (c) PD 3428 in DMF, (d) PD 2410 in ethanol, and (e) PD 824 in DMSO.

Fig. 7
Fig. 7

(a) Nanosecond Z-scan results for PD 2410 in ethanol at fluences of 5.8 × 10 3 J cm 2 (circles), 11.5 × 10 3 J cm 2 (triangles), and 23 × 10 3 J cm 2 (squares); fitting parameters of σ 10 = 1.2 × 10 16 cm 2 , σ 12 = 3.8 × 10 16 cm 2 , and τ 10 = 1.2 ns . (b) Comparison of the excited-state cross sections determined by the picosecond (circles) and nanosecond (squares) Z scans using the three-level model for PD 1952 plotted as a function of solvent viscosity.

Fig. 8
Fig. 8

(a) Nanosecond nonlinear transmission curves with fits for PD 824 in PC using the four-level model (dashed curve) and new six-level model (solid curve) shown in (b); (b) Six-level model to fit nanosecond nonlinear transmission curves composed of the four-level model with a new decay pathway from the first excited state to a cis state ( C 1 ) .

Fig. 9
Fig. 9

Nanosecond nonlinear transmission curves with the 7 ns pulse width (FWHM) with fits using the four-level model (dashed curves) and six-level model without absorption from the cis state (solid curves) for (a) PD 2350 in DMF, (b) PD 1952 in ethanol, (c) PD 3428 in butanol, (d) PD 2410 in methanol, and (e) PD 824 in PC.

Fig. 10
Fig. 10

Nanosecond nonlinear transmission curves using a 21 ns pulse width (FWHM) with fits using the six-level model without absorption from the cis state (solid curves) and the six-level-model with absorption out of the cis state (dashed curves) for (a) PD 2350, (b) PD 1952, (c) PD 3428, (d) PD 2410, and (e) PD 824 in ethanol. PDs 2350 and 2410 can be fitted with σ 45 = 0 . For PD 1952 σ 45 = 2.4 × 10 17 cm 2 , for PD 3428 σ 45 = 5.0 × 10 17 cm 2 , and for PD 824 σ 45 = 7.9 × 10 17 cm 2 .

Fig. 11
Fig. 11

ESA spectra for (a) PD 2350, (b) PD 1952, (c) PD 3428, (d) PD 2410, (e) PD 824, and (f) PD 1659 in ethanol. Solid curves are the linear absorption spectra, and dotted curves are the ESA spectra.

Fig. 12
Fig. 12

Analysis of ESA spectra plotted as a function of conjugation length from dicarbocyanine to pentacarbocyanine dyes: (a) peak of linear (squares) and ESA (circles) spectra, (b) FWHM (inverse centimeters) of linear (squares) and ESA (circles) absorption bands, (c) integrated areas of linear (squares) and ESA (circles) absorption bands, and (d) ratio of integrated areas of ESA to linear absorption bands.

Fig. 13
Fig. 13

Excited-state lifetime as a function of conjugation length for dicarbocyanine to pentacarbocyanine in ethanol.

Fig. 14
Fig. 14

Δ ν versus polarity for PD 3428 (squares), PD 2350 (circles), and PD 1952 (triangles) with fits using the Lippert–Mataga equation. Fit parameter a = 6.4 Å for PD 3428, a = 4.5 Å for PD 1952, and a = 4.8 Å for PD 2350.

Fig. 15
Fig. 15

Orientational diffusion times and fits with a stick boundary condition (solid curves) and slip boundary condition (dotted lines) for (a) PD 1952 and (b) PD 2350.

Fig. 16
Fig. 16

Analysis of ground-state and ESA cross sections. (a) Ground-state (squares) and excited-state (circles) cross sections for PD 1952 in all host solvents plotted as a function of viscosity. (b) Peak ground-state cross section (squares) and excited-state cross section (circles) as a function of conjugation length (dicarbocyanine PD 2350, tricarbocyanine PD 3428, tetracarbocyanine PD 824, pentacarbocyanine PD 1659); all dyes in ethanol.

Fig. 17
Fig. 17

(a) Experimental picosecond nonlinear transmission results for PD 2350 (triangles), PD 1952 (filled squares), PD 2410 (open squares), PD 3428 (open circles), and PD 824 (filled circles) in DMSO. (b) Picosecond nonlinear transmission using peak parameters for the five dyes in ethanol—PD 2350 (circles): α 500 = 46 , β 500 = 9 ; PD 1952 (solid curve): α 532 = 84 , β 532 = 7 ; PD 2410 (triangles): α 594 = 3.2 , β 594 = 0.9 ; PD 3428 (dashed curve): α 532 = 50 , β 532 = 6 ; PD 824 (squares): α 570 = 23 , β 570 = 3.5 .

Fig. 18
Fig. 18

(a) Experimental nanosecond nonlinear transmission results for PD 2350 (triangles), PD 1952 (closed squares), PD 2410 (open squares), PD 3428 (open circles), and PD 824 (closed circles) in ethanol. (b) Nanosecond nonlinear transmission using peak parameters for the five dyes in methanol—PD 2350 (circles): α 500 = 46 , β 500 = 9 ; PD 1952 (solid curve): α 532 = 84 , β 532 = 7 ; PD 2410 (triangles): α 594 = 3.2 , β 594 = 0.9 ; PD 3428 (dashed curve): α 532 = 50 , β 532 = 6 ; PD 824 (squares): α 570 = 23 , β 570 = 3.5 .

Tables (5)

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Table 1 Chemical Names and Molecular Structure Information

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Table 2 Key Parameters for Protic and Aprotic Solvents

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Table 3 Excited-State Dynamics

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Table 4 Nonlinear Absorption Properties

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Table 5 Molecular Parameters Determined from Experiments and Fits

Equations (11)

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Δ ν = ν a ν f = 2 h c ( Δ μ e g ) 2 a 3 Δ f + const. ,
N 0 t = σ 01 I ω N 0 + N 1 τ gr + N 5 τ 40 ,
N 1 t = σ 01 I ω N 0 ( 1 τ gr + σ 12 I ω + 1 τ 14 ) N 1 + N 2 τ 21 ,
N 2 t = σ 12 I ω N 1 N 2 τ 21 ,
N 4 t = N 1 τ 14 ( σ 45 I ω + 1 τ 40 ) N 4 + N 5 τ 54 ,
N 5 t = σ 45 I ω N 4 N 5 τ 54 ,
I z = I ( σ 01 N 0 + σ 12 N 1 + σ 23 N 2 + σ 45 N 4 ) ,
1 τ 10 = 1 τ 14 + 1 τ gr .
τ r = η V K T f C bnd + τ DF ,
f = 2 3 1 ρ 4 ( 2 ρ 2 ) ρ 2 1 ρ 2 ln ( 1 + 1 ρ 2 ρ ) ρ 2 ρ < 1 ,
τ DF = μ 2 9 a 3 k T ( n 2 + 2 ) 2 [ ϵ ( 0 ) n 2 ] [ 2 ϵ ( 0 ) + n 2 ] 2 τ D ,

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