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  • 1
    Electronic Resource
    Electronic Resource
    Microscopic solvation dynamics and solvent-controlled electron transfer (1990)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 94 (1990), S. 8557-8561 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100386a014
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  • 2
    Electronic Resource
    Electronic Resource
    Photoinjection into electrolyte solutions. The role of thermalization (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 2975-2979 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photoinjection of low-energy electrons from a metal electrode into electrolyte solution is analyzed. Screening of the image potential during the emission and thermalization stages is neglected. Observed deviations from the Fowler law are associated with the energy dependence of the electron thermalization distance. Thermalization of injected electrons is treated assuming nonlocal energy loss to librations and phonons (the Fröhlich–Platzman model) and diffusive dynamics. The value of the exponent in the photoinjection law is predicted to be α=2.75 for Debye solvents. The measured photocurrent scales linearly with the Debye relaxation time of the solution. The theory describes isotope effect on photoinjection into aqueous electrolyte solutions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.460899
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  • 3
    Electronic Resource
    Electronic Resource
    Thermalization of photoelectrons in polar medium (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4495-4508 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The process of thermalization of a hot subexcitation photoelectron in polar medium is studied. The master equation is used as a starting point to derive analytic expression for the thermalization distances distribution function. The resulting expression depends upon the mechanism of energy dissipation via the first two moments of the energy loss probability. Asymptotic decay of the distribution with the distance depends on the character of electron motion (exponential for the ballistic motion; Gaussian for the diffusion). A general scheme was developed for evaluation of the energy loss probability within the framework of the linear response theory. Explicit results are derived for electron thermalization in polar medium whose dissipative properties are characterized by the Debye macroscopic dielectric susceptibility function (the Fröhlich–Platzman model). Comparison of the estimates of thermalization distance in water with the experiment shows that the randomization of the direction of the electron motion is much faster than the thermalization process. The dependence of the most probable (average) thermalization distance on the initial kinetic energy, En, and on the dielectric relaxation time, τD, is found for the ballistic and the diffusive motion of the electron (∝E3/4nτ 1/2D for diffusive motion). An explicit relation is derived between the probability to escape geminate recombination and the excess kinetic energy as well as the polarity of the medium and its relaxation time. Results are used to interpret the recent experimental data on the yield and kinetics of geminate recombination in normal and heavy water.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.460605
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  • 4
    Electronic Resource
    Electronic Resource
    Ion solvation in clusters (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 536-546 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Solvent size effects on ion solvation in clusters of polar molecules are explored. Expressions for the adiabatic and the vertical solvation energies of an ion imbedded in a cluster are derived within the framework of the mean-spherical approximation (MSA). The short-range order in the finite system is assumed to be similar to that in the bulk liquid, allowing to use the bulk MSA pair correlation function. The solvent shell structure is manifested in the size dependence of the solvation energy for several (4–5) solvent shells. The hydration energies and the vertical electron photodetachment threshold energies of halide anions in water clusters were evaluated. The bulk values of these physical parameters for large anions (I− and Br− ) are in good agreement with experimental data. The predicted size dependence of the vertical photodetachment threshold, Iv(n), is in good agreement with experimental data for the small I(H2O)−n clusters (1≤n≤15). For intermediate sized clusters (12≤n≤50) the theory predicts plateaus and local minima in the absolute values of solvation energy and Iv(n) due to the parallel solvent dipoles alignment in the distant solvation shells. For large clusters (n〉125) the finite size correction to the solvation energy scales inversely with the cluster size (∝n−1/3). This behavior, as well as the value of the slope, are in agreement with the prediction of the continuum dielectric (CD) model. The absolute values of the solvation energy and Iv(n) predicted by MSA are significantly lower than within the CD model.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463601
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  • 5
    Electronic Resource
    Electronic Resource
    Solvation dynamics in polar liquids (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 4288-4299 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ion and dipole solvation kinetics is studied within the framework of the mean-spherical approximation (MSA). The solvation dynamics in nonassociated polar solvents involves a hierarchy of relaxation times in accordance with Onsager's "inverted snowball'' picture. The average solvation time is determined by the relative solvent and solute sizes and by the dynamic screening. The dipole solvation is slower than ion solvation due to the shorter spatial range of interaction. The theoretical results are confronted with experimental data on time-resolved fluorescence shifts of dipolar probe molecules in nonassociated polar solvents. The experimental kinetic data exhibit a crossover from a short-time dipole solvation behavior to ion solvation at intermediate and long times. For associated polar solvents the Onsager picture has to be modified to account for structure breaking in the first solvation shell(s).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.454811
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  • 6
    Electronic Resource
    Electronic Resource
    Erratum: Dynamics of ionic solvation [J. Chem. Phys. 88, 3246 (1988)] (1989)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 611-611 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.456714
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  • 7
    Electronic Resource
    Electronic Resource
    Dynamics of ionic solvation (1988)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 3246-3252 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Dynamics of solvation in simple polar liquids is studied within the framework of the mean spherical approximation. Exact results are derived for the Born solvation energy and for the correlation function for the solvation time of an instantaneously formed ion (or dipole) in a polar solvent. The results are in qualitative agreement with the recent approximate treatment by P. Wolynes [J. Chem. Phys. 86, 5133 (1987)]. Implications of the results for the solvation dynamics of dipoles and of excess electrons in polar solvents are considered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453920
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  • 8
    Electronic Resource
    Electronic Resource
    A numerical test of activated rate theories for cusped and smooth potentials (1996)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 6547-6559 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A numerical study of the effect of dissipation on the radiationless transition rate in the adiabatic and solvent-controlled limits is presented. For light particle reactions, the nonlinearity of the potential surface in the vicinity of the barrier top is important, and the potential may be approximated as a cusped double well potential, provided that the nonadiabatic coupling is small compared to the thermal energy. Three different theoretical approaches for calculation of the thermally activated rate are analyzed and compared with exact numerical results. We find that Variational Transition State Theory (VTST) with a planar dividing surface, as well as the approach of Calef and Wolynes (CW), provide a good description of the rate of symmetric reactions. A rate expression suggested by Dekker is found to be the least accurate. The CW approach is most accurate in the strong damping regime, while VTST is better in the weak damping regime. The accuracy of both methods improves as the potential is smoothed. VTST and the CW expression are also found to give a reasonable description of asymmetric reactions, provided that the asymmetry is not too large. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.471374
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  • 9
    Electronic Resource
    Electronic Resource
    Variational transition state theory for curve crossing processes: A uniform rate expression (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 103 (1995), S. 7912-7926 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new approach is suggested for evaluation of the radiationless transition rate for the curve-crossing problem in the presence of dissipation. The rate is evaluated by using the conventional Landau–Zener theory but for a collective system–bath coordinate, which is characterized by a maximal mean-free path in the vicinity of the crossing point. Variational transition state theory (TST) is employed for determination of this quasiballistic mode. The resulting uniform rate expression bridges between the known nonadiabatic, solvent controlled and TST limits. The main effect of dissipation is the reduction of the slope difference of the potential of mean force along the quasiballistic mode compared to that along the original reaction coordinate. This results in an increase of the reaction adiabaticity. Application of the theory is illustrated for the symmetric normal crossing of two parabolic diabatic terms with Ohmic dissipation. Explicit results for the rate in the relevant physical limits are derived. The theory is also used to analyze resonant electron transfer reactions in Debye solvents. © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.470209
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  • 10
    Electronic Resource
    Electronic Resource
    Cage Effect on the Diffusion-Controlled Recombination Kinetics (1994)
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 98 (1994), S. 3412-3416 
    Details
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/j100064a023
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