Electron-transfer times are not equal to longitudinal relaxation times in polar aprotic solvents

Kahlow, Michael A.; Kang, Tae June; Barbara, Paul F.

doi:10.1021/j100310a005

Cited by 144 publications

(108 citation statements)

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“…Thus the shorter time scale measurements are consistent with our previous results which showed that r~ decreases as the temperature increases. For the solvents used in the current experiments, only in the case of ethylacetate our results can be compared with the ultrafast dynamics studies reported elsewhere [22,23]. The solvation times for ethylacetate obtained elsewhere [22,24] are 2.3 ps (coumarin 311) and 2.6 ps (coumarin 102), respectively.…”

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

confidence: 55%

“…For the solvents used in the current experiments, only in the case of ethylacetate our results can be compared with the ultrafast dynamics studies reported elsewhere [22,23]. The solvation times for ethylacetate obtained elsewhere [22,24] are 2.3 ps (coumarin 311) and 2.6 ps (coumarin 102), respectively. Comparing these values with the results of Table 2 it is seen that the magnitude of r~ for fluoroprobe in ethylacetate is in good agreement with the results of Barbara's group.…”

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

confidence: 55%

“…A rough estimate of the photoexcited excess vibrational energy in the excited singlet state is about 10,000 cm -L. As can be seen from Table 2, the solvation time for fluoroprobe dissolved in ethylacetate is 2.7 ps. Previously, the solvation dynamics of coumarin 102, also dissolved in ethylacetate, was determined to be 2.6 ps [22,23]. In the latter experiment, the excess vibrational energy was about a few thousand cm-1.…”

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

confidence: 92%

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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 Howmentioning

confidence: 55%

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

confidence: 55%

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

confidence: 92%

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Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

et al. 1996

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“…Solvent is coupled by changes in local electric fields that accompany electron transfer (Ulstrup 1979;Dogonadze et al 1985;Reichardt 1988;Chen & Meyer 1998). Dynamics of solvent coupling have been measured by observing absorption band shifts following ultrafast laser excitation of charge transfer transitions (Kahlow et al 1987;Horng et al 1995;Fleming & Cho 1996).…”

Section: It Icmentioning

confidence: 99%

Probing the localized-to-delocalized transition

Concepcion

Dattelbaum

Meyer

et al. 2007

Phil. Trans. R. Soc. A.

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Detailed understanding of the transition between localized and delocalized behaviour in mixed valence compounds has been elusive as evidenced by many interpretations of the Creutz-Taube ion, [(NH 3 ) 5 Ru(pz)Ru(NH 3 ) 5 ] 5C . In a review in 2001, experimental protocols and a systematic model to probe this region were proposed and applied to examples in the literature. The model included: (i) multiple orbital interactions in ligand-bridged transition metal complexes, (ii) inclusion of spin-orbit coupling which, for dp 5 -dp 6 complexes, leads to five low-energy bands, two from interconfigurational (dp/dp) transitions at the dp 5 site and three from intervalence transfer transitions, (iii) differences in time scale between coupled vibrations and solvent modes which can result in solvent averaging with continued electronic asymmetry defining 'class II-III', an addition to the Robin-Day classification scheme, and (iv) delineation of coupled vibrations into barrier vibrations and 'spectator' vibrations. The latter provide direct insight into localization or delocalization and time scales for electron transfer. In this paper, the earlier model is applied to a series of mixed-valence molecules.

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“…[32][33][34][35] Most of the experimental data on solvation dynamics in polar solvents have been obtained using a time-resolved fluorescence method with upconversion. [36][37][38][39][40][41][42][43][44][45][46] The energy difference in the ground and excited electronic states of the solute is manifested through (t), the frequency of the fluorescence spectral maximum of the molecule. Its timeevolution ͑dynamic Stokes shift, DSS͒ reflects the solvation dynamics of the electronically excited solute.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Stokes shift in solution: Effect of finite pump pulse duration

Georgievskii

Hsu

Marcus

1998

The Journal of Chemical Physics

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The time-evolution of the fluorescence spectrum of a dissolved chromophore excited by an ultrafast pump pulse is considered. The average value of the energy difference of the solute in its excited and ground states is used to describe the relaxation of the maximum of the transient fluorescence spectrum to its equilibrium value ͑dynamic Stokes shift, DSS͒. A simple formula for the normalized DSS is obtained which generalizes an earlier standard classical expression and includes the effect of a pump pulse of finite duration. As an example, dielectric dispersion data are used for a dipolar solute in water to estimate the quantum correction to the standard DSS expression. The correction is negligible when the frequency of the pump pulse is close to the maximum in the absorption spectrum, but a deviation from the standard formula can be expected for the pump pulse tuned to a far wing of the absorption band of the chromophore. An expression is given for this deviation.

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Electron-transfer times are not equal to longitudinal relaxation times in polar aprotic solvents

Cited by 144 publications

References 0 publications

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

Subpicosecond studies of the solvation dynamics of fluoroprobe in liquid solution

Probing the localized-to-delocalized transition

Dynamic Stokes shift in solution: Effect of finite pump pulse duration

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