Abstract
Fluorescence quenching of a pyrylium salt (PDP2+) by toluene in acetonitrile gives rise to a nonexponential decay. This behavior is ascribed to the so-called transient effect occurring at high quencher concentrations for diffusion-controlled reactions. First, the Kalman filter was used to deconvolute the original signal from the experimental decay curve and the response function of the apparatus. This treatment led to a calculated deconvoluted decay curve which enabled the transient effect analysis to be conducted. This real decay curve was then analyzed using two models. The Smoluchowski—Collins—Kimball (SCK) model, applied to diffusion-controlled reactions, yielded the reaction radius r AD and the intrinsic rate constant k act of the bimolecular electron transfer reaction. The Marcus electron transfer/diffusion (ETD) model, which provides a powerful method to evaluate the electronic coupling H el associate with the reaction, was also used but is more difficult to handle due to extensive computational needs. Finally, the adequacy of the two models (SCK and ETD) for analysis of the transient effect was addressed, as well as the appropriateness of the Kalman filter for fluorescence signal deconvolution.
Similar content being viewed by others
References
R. A. Marcus (1956) J. Chem. Phys. 24, 966.
R. A. Marcus and N. Sutin (1985) Biochim. Biophys. Acta 811, 265.
I. R. Gould, D. Ege, and S. L. Mattes (1987) J. Am. Chem. Soc. 109, 3794.
N. Mataga, T. Asahi, Y. Kanda, T. Okada, and T. Kakitani (1988) Chem. Phys. 127, 249.
E. Vauthey, P. Suppan, and E. Haselbach (1988) Helv. Chim. Acta 71, 93.
J. M. Chen, T. I. Ho, and C. Y. Mou (1990) J. Phys. Chem. 94, 2889.
D. M. Guldi and K. D. Asmus (1997) J. Am. Chem. Soc. 119, 57.
D. Rehm and A. Weller (1970) Isr. J. Chem. 8, 259.
A. Weller (1961) Prog. React. Kinet. 1, 188.
R. M. Noyes (1961) Prog. React. Kinet. 1, 129.
S. A. Rice (1985) Comprehensive Chemical Kinetics, Vol 25. Diffusion Limited. Reactions, Elsevier, New York.
J. C. Andre, M. Niclause, and W. R. Ware (1978) Chem. Phys. 28, 371.
S. Nishikawa, T. Asahi, T. Okada, N. Mataga, and T. Kakitani (1991) Chem. Phys. Lett. 185, 237.
T. Kakitani, A. Yoshimori, and N. Mataga (1992) J. Phys. Chem. 96, 5385.
P. Jacques and X. Allonas (1995) Chem. Phys. Lett. 233, 533.
X. Allonas and P. Jacques (1997) Chem. Phys. 215, 371.
S. Murata, M. Nishimura, S. Y. Matsuzaki, and M. Tachiya (1994) Chem. Phys. Lett. 219, 200.
T. Niwa, K. Kikuchi, N. Matsusita, M. Hayashi, T. Katagiri, Y. Takahashi, and T. Miyashi (1993) J. Phys. Chem. 97, 11960.
S. Murata, S. Y. Matsuzaki, and M. Tachiya (1995) J. Phys. Chem. 99, 5354.
S. F. Swallen, K. Weidemaier, H. L. Tavernier, and M. D. Fayer (1996) J. Phys. Chem. 100, 8106.
S. Tripathi, V. Wintgens, P. Valat, V. Toscano, and J. Kossanyi (1987) J. Luminesc. 37, 149.
P. Jacques, D. Burget, and X. Allonas (1996) New J. Chem. 20, 233.
D. V. O'Connor, W. R. Ware, and J. C. Andre (1979) J. Phys. of Chem. 83, 1333.
J. C. Andre, L. M. Vincent, D. V. O'Connor, and W. R. Ware (1979) is J. Phys. Chem. 83, 2285.
A. E. McKinnon, A. G. Szabo, and D. R. Miller (1977) J. Phys.
J. R. Lakowicz (1983) Principles of Fluorescence Spectroscopy, Plenum Press, New York.
M. Sikorski, E. Krystkowiak, and R. P. Steer (1998) J. Photochem. Photobiol. A Chem. 117, 1.
M. Sikorski, W. Augustiniak, I. V. Khmelinskii, and F. Wilkinson (1996) J. Luminesc. 69, 217.
M. Van Zegel, N. Boens, D. Daems, and F. C. De Schryver (1986) Chem. Phys. 101, 311.
R. Das and N. Periasamy (1989) Chem. Phys. 136, 361.
A. Gelb, J. F. Kasper, R. A. Nasdh, C. F. Price, and A. A. Sutherland (1974) Applied Optimal Estimation, MIT Press, Cambridge, MA
N. V. Ahmed (1988) Element of Finite Dimensional Systems and Control Theory John Wiley & Sons, New York, Longman Group UK Ltd., Longman House, Burut Hill, Harlow.
F. C. Collins and G. E. Kimball (1949) J. Colloid Sci. 4, 425.
The ground-state geometry of PDP2+ was optimized by using the MNDO Hamiltonian from the Hyperchem package (Hypercube Inc., Canada). The radius was then derived from the calculation of the volume using a grid method.
D. W. Marquardt (1993) J. Soc. Indust. Appl. Math. 11, 431.
L. Burel, M. Mostafavi, S. Murata, and M. Tachiya (1999) J. Phys. Chem. 103, 5882.
G. M. Brown and N. Sutin (1979) J. Am. Chem. Soc. 101, 883.
M. Tachiya (1983) Radiat. Phys. Chem. 21, 167.
L. Song, S. F. Swallen, R. C. Dorfman, K. Weidemaier, and M. D. Fayer (1996) J. Phys. Chem. 97, 1374.
S. F. Swallen, K. Weidemaier, and M. D. Fayer (1996) J. Chem. Phys. 104, 2976.
H. Sano and M. Tachiya (1979) J. Chem. Phys. 71, 1276.
From ISML library, trademark of Visual Numerics Inc., Hous-ton, TX.
G. J. Kavarnos and N. J. Turro (1986) Chem. Rev. 86, 401.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Allonas, X., Jacques, P., Accary, A. et al. Deriving Intrinsic Parameters of Photoinduced Electron Transfer Reaction from the Transient Effect Probed by Picosecond Time-Resolved Fluorescence Quenching. Journal of Fluorescence 10, 237 (2000). https://doi.org/10.1023/A:1009424521742
Issue Date:
DOI: https://doi.org/10.1023/A:1009424521742