Gilbert C. Walker, Wlodzimierz Jarzeba, Tai Jong Kang, Alan E. Johnson, and Paul F. Barbara, "Ultraviolet femtosecond fluorescence spectroscopy: techniques and applications," J. Opt. Soc. Am. B 7, 1521-1527 (1990)
Because of important improvements made to the UV-region femtosecond emission apparatus at the University of Minnesota, it is now possible to record the UV fluorescence of organic molecules with an effective resolution reaching ~50 fsec and a useful signal-to-noise ratio. Applications of this technology to two fundamental processes in chemistry (solvation and electron transfer) are briefly described. Molecular examples include (i) the solvation probes Coumarin 152 and Coumarin 343 and (ii) the electron-transfer molecules 9,9′-bianthryl and 4-(9-anthryl)-N,N′-dimethylaniline.
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At room temperature with a Coumarin 152 probe, in picoseconds.
See Ref. 2 for details of this type of calculation.
The error in 〈τS〉is approximately 20%. The error in the individual components of the biexponential fit to C(t) is larger.
From measurements of Kahlow et al.2
DMF is N, N-dimethylformamide; DMSO is dimethyl sulfoxide; measured by the linear wavelength method2,13 at 470 nm.
Table 2
Comparison of Experimental and Theoretical Solvation Times in Aqueous Solution (psec)
Measured at 420 nm; in picoseconds. With the exception of acetone, the fluorescence decay is fitted to a biexponential mode, 〈τET〉 is calculated by weighting the two components by their amplitudes and adding.
Dimethyl sulfoxide.
Table 4
Comparison of 〈τET〉 and 〈τS〉 for ADMA in Various Solvents (psec)
These times are derived by fitting the fluorescence transients of ADMA at 433 nm to a single exponential decay.
See Table 1. N,N-Dimethylformanide.
Dimethyl sulfoxide.
Tables (4)
Table 1
Comparison of Solvation Data and Dielectric-Continuum Model Calculationsa
At room temperature with a Coumarin 152 probe, in picoseconds.
See Ref. 2 for details of this type of calculation.
The error in 〈τS〉is approximately 20%. The error in the individual components of the biexponential fit to C(t) is larger.
From measurements of Kahlow et al.2
DMF is N, N-dimethylformamide; DMSO is dimethyl sulfoxide; measured by the linear wavelength method2,13 at 470 nm.
Table 2
Comparison of Experimental and Theoretical Solvation Times in Aqueous Solution (psec)
Measured at 420 nm; in picoseconds. With the exception of acetone, the fluorescence decay is fitted to a biexponential mode, 〈τET〉 is calculated by weighting the two components by their amplitudes and adding.
Dimethyl sulfoxide.
Table 4
Comparison of 〈τET〉 and 〈τS〉 for ADMA in Various Solvents (psec)
These times are derived by fitting the fluorescence transients of ADMA at 433 nm to a single exponential decay.
See Table 1. N,N-Dimethylformanide.
Dimethyl sulfoxide.
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