Solvation dynamics in ethanol

Su, Shyh Gang; Simon, John D.

doi:10.1021/j100295a008

Cited by 90 publications

(32 citation statements)

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“…These results are similar to other reports of solvent relaxation about excited chromophores in alcohols (32,33,36,41,42,50,53,54). Biphasic relaxation kinetics are typically observed, and one relaxation time is generally comparable to Tl1.…”

Section: Ru(bpy)2(cn)2supporting

confidence: 91%

Solvent Reorganization Energetics and Dynamics in Charge-Transfer Processes of Transition Metal Complexes

Zhang

Kozik

Sutin

et al. 1991

Advances in Chemistry

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Time-resolved and steady-state luminescence measurements were used to probe the energetics and dynamics of solvation in two different transition metal complexes. The metal-to-ligand charge-transfer excited state of Ru(bpy)2(CN)2 (bpy is bipyridine) was studied in a series of aliphatic alcohols, and the luminescent excited state of Mo2Cl4[P(CH3)3]4 was studied in aprotic organic solvents. The energetics of excited-state solvation were evaluated from the shapes and positions of the steady-state luminescence spectra recorded at low (~10 K) and room temperatures. The dynamics of excited-state solvation were probed by time-resolved emission spectroscopy. THE SOLVENT PLAYS A MAJOR ROLE I N GOVERNI NGthe rates of electrontransfer reactions in solution (I, 2). The solvent reorganization associated with electron-transfer reactions in polar solvents is often the major contributor to the total reorganization energy (X). In recent years, questions have arisen regarding the importance of solvent reorganization dynamics in controlling the rates of fast electron-transfer processes (3-11). Models that treat the solvent as a continuous dielectric medium are often used to describe solvation energetics and dynamics, but the applicability of these models to real chemical systems remains an open question. Electronic absorption and emission spectroscopies are powerful techniques for probing the environments of molecules in solution (12-22). The energies and shapes of absorption

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Section: Ru(bpy)2(cn)2supporting

confidence: 91%

Solvent Reorganization Energetics and Dynamics in Charge-Transfer Processes of Transition Metal Complexes

Zhang

Kozik

Sutin

et al. 1991

Advances in Chemistry

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“…Fig. 10 shows the dependence of Tobs/'tL on eo for all the systems we have studied plus several from the literature [33,34]. For TL only the longest longitudinal time is used TL = TLI = (e:<;l/eod TOI' The dashed line represents the continuum theory prediction of Refs.…”

Section: Discussionmentioning

confidence: 99%

The Dynamics of Polar Solvation

Castner

Bagchi

Maroncelli

et al. 1988

Ber Bunsenges Phys Chem

105

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Fluorescence upconversion experiments with subpicosecond resolution are described. The time dependent fluorescence spectra of several probe molecules In polar solvents are measured and used to construct the Stokes shift correlation function C(I). The correlation functions decay nonexponentially in contrast to the predictions of simple Debye/Onsager continuum theory. At high values of the static dielectric onstants the solv~tion times are much slo~er th.an predicted from standard continuum theory. Generalizations of continuum theory to mclude non-spherical shapes, non~Debye ?l~lectrIc response and saturation effects are discussed. The experimental data are qualitatively In accord With predictions based on a frequency and position dependent dielectric response.

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“…[1][2][3][4][5][6][7] In the past few years, several techniques have been applied to investigate solvation dynamics. Fluorescence upconversion measurements have been nicely combined with molecular dynamics simulations in series of papers by Maroncelli's and Fleming's groups.…”

Section: Introductionmentioning

confidence: 99%

Effect of Fluorescence Quenching by Stimulated Emission on the Spectral Properties of a Solvent-Sensitive Fluorophore

et al. 1996

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We examined the emission spectra and wavelength-dependent anisotropies of the solvent-sensitive fluorophore 4-(dimethylamino)-4′-cyanostilbene (DCS) under condition of fluorescence quenching by stimulated emission. The sample was illuminated with a train of 10 ps pulses at 285 nm, and a train of stimulating pulses at 570 nm which were delayed by a time t d relative to the excitation. Stimulated emission of DCS was demonstrated to occur by observation of gain in the long-wavelength beam. Illumination on the long-wavelength side of the emission spectrum with the long-wavelength time-delayed pulses resulted in a blue shift of the emission spectrum, and a progressive decrease of the emission anisotropy as the observation wavelength increased toward the stimulating wavelength. The spectral shifts and wavelength-dependent anisotropies of DCS were more pronounced in more viscous solvents where spectral relaxation is incomplete during the excited state lifetime. Light quenching of DCS in a low-viscosity solvent revealed no spectral shifts or wavelengthdependent anisotropies. Control measurements using acridine orange, which is relatively insensitive to solvent polarity, did not show any spectral shift or wavelength-dependent anisotropy with light quenching. The data for DCS can be explained by the presence of a time-dependent spectral shift and wavelength-selective quenching of the longer wavelength emission. In this model the relaxed state is formed following excitation of the unrelaxed state, and the relaxed state is preferentially quenched by long-wavelength illumination. Comparison of the data with model calculations indicates the presence of at least two spectral relaxation times. These results demonstrate that light quenching by stimulated emission acts selectively based on overlap of the stimulating wavelength with the emission spectrum. Observation of the emission spectrum in the presence of time-delayed and power-controlled long-wavelength pulses can be used to study time-dependent excited state processes.

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Solvation dynamics in ethanol

Cited by 90 publications

References 0 publications

Solvent Reorganization Energetics and Dynamics in Charge-Transfer Processes of Transition Metal Complexes

Solvent Reorganization Energetics and Dynamics in Charge-Transfer Processes of Transition Metal Complexes

The Dynamics of Polar Solvation

Effect of Fluorescence Quenching by Stimulated Emission on the Spectral Properties of a Solvent-Sensitive Fluorophore

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