Inhomogeneous decay kinetics and apparent solvent relaxation at low temperatures

Fee, R. S.; Milsom, John A.; Maroncelli, Mark

doi:10.1021/j100166a048

Cited by 61 publications

(44 citation statements)

References 2 publications

(3 reference statements)

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“…The excellent fit shows that virtually a v3,~ -law is obeyed for the fluoroprobe/diethylether system in agreement with previous measurements on a picosecond time scale [18]. Previously the time-dependence of the integrated intensity of the fluorescence of in a few coumarine molecules has been considered [31,32]. A v3-type relationship was found in case homogeneous line broadening prevails, whereas inhomogeneous line broadening effects give rise to a deviation of the v 3 dependence.…”

Section: C(t) Is Considered To Discuss the Stokes Shift Dynamics Howsupporting

confidence: 88%

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

et al. 1996

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The dynamic Stokes shift of fluoroprobe in its lowest excited charge transfer state has been studied in a series of solvents, at room temperature, with a time resolution of about 300 fs. Using the fluorescent upconversion method dynamic Stokes shifts of up to 3000 cm ~ have been resolved. The Stokes shift is attributed to the solvent response to the large photoinduced dipole moment of fluoroprobe (~ 30 D) in the fluorescent charge transfer state. The solvation dynamics is determined by the rotational diffusional motions of the ethereal solvent molecules.

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Section: C(t) Is Considered To Discuss the Stokes Shift Dynamics Howsupporting

confidence: 88%

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

et al. 1996

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“…Inhomogeneous broadening in this case is static and time-dependent effects absent (42). However, apparent time-dependent motions of spectra in these cases have been reported (104). The origin of these motions is not relaxation but inhomogeneous decay kinetics, which make the decay longer at longer wavelengths, therefore the reconstructed spectra may demonstrate apparent shift as a function of time (105).…”

Section: Application Of Red-edge Effects Liquid Viscous and Glass-fomentioning

confidence: 84%

“…The theory predicts that in the case of Debye dielectric relaxation C(t) = exp (Àt-t R ) should be exponential (Eqns 5 and 6). The problem is that the apparent shifts in time-resolved spectra can be observed not only in the case of spectral relaxations but also in the case of heterogeneous decay (104,105). The latter is the decay occurring in a population of species, which differ both in l em and t i .…”

Section: Analysis Of Time-resolved Datamentioning

confidence: 99%

The red‐edge effects: 30 years of exploration

2002

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In 1970, three laboratories independently made a discovery that, for aromatic fluorophores embedded into different rigid and highly viscous media, the spectroscopic properties do not conform to classical rules. The fluorescence spectra can depend on excitation wavelength, and the excited-state energy transfer, if present, fails at the "red" excitation edge. These red-edge effects were related to the existence of excited-state distribution of fluorophores on their interaction energy with the environment and the slow rate of dielectric relaxation of this environment. In these conditions the site-selection can be provided by variation of the energy of illuminating light quanta, and the behaviour of selected species can be followed as a function of time and other variables. These observations found extensive application in different areas of research: colloid and polymer science, molecular biophysics, photochemistry and photobiology. In particular, they led to the development of very productive methods of studying the dynamics of dielectric relaxations in protein and membranes, using the tryptophan emission and the emission of a variety of probes. These studies were extended to the time domain with the observation of new site-selective effects in emission intensity and anisotropy decays. They stimulated the emergence and development of cryogenic energy-selective and single-molecular techniques that became valuable tools in their own right in chemistry and biophysics research. Site-selection effects were discovered for electron-transfer and proton-transfer reactions if they depended on the dynamics of the environment. This review is focused on the progress in the field of red-edge effects, their applications and prospects.

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“…Moreover, the dynamics slows down at lower temperature (see Table 1) and, given the time resolution in the present experiments, a progressively larger fraction of the total dynamical Stokes shift becomes accessible experimentally as the temperature is reduced. An estimate of the influence of our limited time resolution on the magnitude of the observed total dynamical Stokes shift may be obtained as follows [45,46]. The solvent's contribution to the total dynamical Stokes shift can be calculated by comparing the energy difference between the maxima of the (steady state) absorption and emission spectra in the solvent under investigation with that obtained in a very apolar solvent such as n-hexane [45,46].…”

Section: Picosecond Transientsmentioning

confidence: 99%

“…An estimate of the influence of our limited time resolution on the magnitude of the observed total dynamical Stokes shift may be obtained as follows [45,46]. The solvent's contribution to the total dynamical Stokes shift can be calculated by comparing the energy difference between the maxima of the (steady state) absorption and emission spectra in the solvent under investigation with that obtained in a very apolar solvent such as n-hexane [45,46]. In this way, we find that the dynamical Stokes shift in diethylether amounts to about 7000 to 8000 cm -1, depending on the temperature.…”

Section: Picosecond Transientsmentioning

confidence: 99%

Picosecond time-dependent Stokes shift studies of fluoroprobe in liquid solution

et al. 1995

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We report on a picosecond spectroscopic study of the dynamical Stokes shift of fluoroprobe in the lowest excited state in the solvents diethylether and ethylacetate. Time-resolved emission spectra with a time-resolution of approximately 10 ps are presented. The spectra reflect dynamical Stokes shifts of a few thousand wave numbers within 10-100 ps after the pulsed laser excitation. The time-dependent shifts are representative of the solvation dynamics of fluoroprobe in diethylether and ethylacetate.

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Inhomogeneous decay kinetics and apparent solvent relaxation at low temperatures

Cited by 61 publications

References 2 publications

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

The red‐edge effects: 30 years of exploration

Picosecond time-dependent Stokes shift studies of fluoroprobe in liquid solution

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