Microscopic solvation dynamics and solvent-controlled electron transfer

Rips, Ilya; Klafter, Joseph; Jortner, Joshua

doi:10.1021/j100386a014

Cited by 51 publications

(35 citation statements)

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“…As expected, expression [13] is reduced to relation [6] in the absence of the second equilibrium. It can be written in the new form:…”

Section: Triplex Formation With P-xylenesupporting

confidence: 81%

“…[6]), one can (i) get the maximum value reached by this quantum yield when the concentration of the aromatics is infinitive; (ii) deduce the ratio kE/ky from the intercept of the plot:…”

Section: Exciplex Formationmentioning

confidence: 99%

“…One is deduced from the plot of I/@;" versus 1/[D] according to relation [6] while the other set uses the maximum values measured for the exciplex lifetime (ze,),,, and for the fluorescence quantum yield (Q? ),,,,,.…”

Section: 'mentioning

confidence: 99%

“…In some cases this quenching is accompanied by a weak and broad emission at wavelengths longer than the quenched fluorescence (3)(4)(5). The influence of the solvent on the course of the electron or charge transfer process has been intensively studied in both its theoretical (6)(7)(8)(9)(10) and experimental (1 [1][2][3][4][5][6][7][8][9][10][11][12][13][14] aspects. Ultrafast (up to lOI3 s-I) electron transfer has been shown to occur between excited dyes and weakly polar electron-donating solvent molecules (15).…”

Section: Introductionmentioning

confidence: 99%

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Unusually strong emission from an exciplex formed between benzenoid solvents and dibenzoylmethanatoboron difluoride. Formation of a triplex

Valat¹,

Wintgens²,

Chow³

et al. 1995

Can. J. Chem.

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Benzene derivatives give, in cyclohexane solution, a strongly emitting ( a f up to 0.8) excited complex with dibenzoylmethanatoboron difluoride (DBMBF2). The rate constant k,, for the complex formation varies between 3.5 x lo9 and 2.6 x loL0 M-I s-I depending on the benzene derivative, and the complex emission can already be detected at very low concentrations of the aromatics. This behaviour is different from that found in acetonitrile where the DBMBF2 emission disappeared completely before the new emission of the complex could be detected. The position of the complex emission and its lifetime depend upon the redox potential of the aromatics: the lower the latter, the longer the lifetime and the more the emission is red-shifted. The monotonous increase of the lifetime and of the fluorescence quantum yield of the emission with the concentration of the aromatics has been interpreted on the basis of an equilibrium between the exciplex and excited DBMBF2. The equilibrium constant varies with the electron-donating property of the aromatics, from 2.7 for benzene to 560 M-I for isodurene. A decrease in the excited complex lifetime or in its fluorescence quantum yield is observed in some cases when the aromatics concentration is close to that of the pure solvent. Such behaviour is believed to arise from a new equilibrium resulting from the interaction of the exciplex with a second molecule of the aromatics to form triplex species. A detailed kinetic study has been undertaken in case of p-xylene, and the rate constants of all the processes involved in the double equilibrium have been determined. No basic difference is observed in the rate constant for exciplex formation when a single or double equilibrium is assumed; on the other hand, large discrepancies are found in the exciplex deactivation processes, specially for the back reaction from the exciplex to excited DBMBF2. The equilibrium constants between DBMBF? and the exciplex, on one hand, and between the latter and the triplex are 56.6 and 0.68 M-', respectively, when the concentration of p-xylene in cyclohexane is 3.3 M. Can. J. Chem. 73: 1902Chem. 73: -1913Chem. 73: (1995

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“…As expected, expression [13] is reduced to relation [6] in the absence of the second equilibrium. It can be written in the new form:…”

Section: Triplex Formation With P-xylenesupporting

confidence: 81%

“…[6]), one can (i) get the maximum value reached by this quantum yield when the concentration of the aromatics is infinitive; (ii) deduce the ratio kE/ky from the intercept of the plot:…”

Section: Exciplex Formationmentioning

confidence: 99%

Section: 'mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Unusually strong emission from an exciplex formed between benzenoid solvents and dibenzoylmethanatoboron difluoride. Formation of a triplex

Valat¹,

Wintgens²,

Chow³

et al. 1995

Can. J. Chem.

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“…For the last decade several theoretical approaches in this field have been tested. They include direct MD simulations, [8][9][10][11][12][13][14][15][16][17][18] the computations of spatial pair correlation functions based on interaction site models ͑i.e., statistical equilibrium theories͒, extended to cover time dependence, [19][20][21][22] dynamical developments of the mean spherical approximation ͑MSA͒ [23][24][25] a nonlocal continuum theory, 26 and other semianalytical treatments. 7,[27][28][29][30][31][32][33][34][35] All these approaches represent microscopic molecular solvent theories at various levels of sophistication.…”

Section: Introductionmentioning

confidence: 99%

An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment

Basilevsky

Parsons

Vener

1998

The Journal of Chemical Physics

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A local continuum solvation theory, exactly treating electrostatic matching conditions on the boundary of a cavity occupied by a solute particle, is extended to cover time-dependent solvation phenomena. The corresponding integral equation is solved with a complex-valued frequency-dependent dielectric function ͑͒, resulting in a complex-valued -dependent reaction field. The inverse Fourier transform then produces the real-valued solvation energy, presented in the form of a time correlation function ͑TCF͒. We applied this technique to describe the solvation TCF for a benzophenone anion in Debye ͑acetonitrile͒ and two-mode Debye ͑dimethylformamide͒ solvents. For the Debye solvent the TCF is described by two exponential components, for the two-mode Debye solvent, by three. The overall dynamics in each case is longer than that given by the simple continuum model. We also consider a steady-state kinetic regime and the corresponding rate constant for adiabatic electron-transfer reactions. Here the boundary effect introduced within a frequency-dependent theory generates only a small effect in comparison with calculations made within the static continuum model.

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Salt effects upon the S2O82? + Ru(NH3)5pz2+ electron transfer reaction

Rodrı́guez

López‐Cornejo

Pérez

et al. 1999

Int. J. Chem. Kinet.

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A study of the kinetic salt effects on the oxidation of Ru(NH 3 ) 5 pz 2ϩ (Pirazinepentaammineruthenium (II)) with (Peroxodisulphate) was carried out. The components of 2Ϫ S O 2 8 the experimental rate constant, k obs , were separated, and the true (unimolecular) electron transfer rate constant, k et , is (approximately) obtained. An analysis of the main parameters controlling the variations of k et , the free energies of reaction and reorganization, is made. Both parameters show a compensating behavior, so there are small variations of k et and k obs when salt concentrations change.

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Microscopic solvation dynamics and solvent-controlled electron transfer

Cited by 51 publications

References 1 publication

Unusually strong emission from an exciplex formed between benzenoid solvents and dibenzoylmethanatoboron difluoride. Formation of a triplex

Unusually strong emission from an exciplex formed between benzenoid solvents and dibenzoylmethanatoboron difluoride. Formation of a triplex

An advanced dielectric continuum approach for treating solvation effects: Time correlation functions. I. Local treatment

Salt effects upon the S2O82? + Ru(NH3)5pz2+ electron transfer reaction

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