Manifestation of the dynamic properties of the solvent in electron transfer reactions

The ability of the multichannel stochastic model to adequately describe the basic features of the kinetics of thermal electron transfer is demonstrated. It is shown that the solution-controlled regime can be realized in the normal Marcus region, whereas it is almost completely suppressed in the inverted region by the reorganization of high-frequency vibrational modes. The continuous transition between the two regions in the neighborhood of the activationless is quantitatively described. It is found that the dynamic properties of the solvent manifest themselves not only in the dependence of the electron transfer rate on the medium relaxation time τ _L , but also in the free energy gap law, shifting the position of the maximum effective rate constant to higher reaction exergonicities. This shift depends on the longitudinal relaxation time of the medium. In slow solvents, the maximum rate constant of electron transfer can exceed 1/τ _L by several orders of magnitude.     

A simple model for magnetism in itinerant electron systems

A new lattice model of interacting electrons is presented. It can be viewed as a classical Hubbard model in which the energy associated to electron itinerance is proportional to the total number of possible electron jumps. Symmetry properties of the Hubbard model are preserved. In the half-filled band with strong interaction the model becomes the Ising model. The main features of the magnetic behavior of the model in the one-dimensional and mean-field cases are studied.     

A simple model of a glow discharge electron beam for materialsprocessing

A simple semiempirical model of the electron beam generated by a pulsed cold cathode electron gun has been developed. The model describes analytically the observed self-focusing of the discharge and predicts the dynamical variation of the focal distance, in good agreement with experiments. This effect plays a major role in the determination of the effective duration of the energy pulse. The model was used to conduct simple calculations of energy thresholds for melting of solid materials, giving helpful insight on ranges of operation of this kind of electron gun for its application to material processing. A comparison with available experimental data for Mg₇₀Zn₃₀ samples is given     

Time resolved CIDNP study of electron transfer reactions in proteins and model compounds

Intramolecular electron transfer (IET) from tyrosine to tryptophan cation radicals is investigated using time resolved chemically induced dynamic nuclear polarization (CIDNP) spectroscopy in combination with laser flash photolysis. In both the tryptophan-tyrosine dipeptide and the denatured state of hen lysozyme in aqueous solution, the transformation TrpH⁺ → TyrO by IET leads to an increase in the tyrosine radical concentration, growth in the tyrosine CIDNP signal, fast decay of the tryptophan CIDNP, and inversion of the phase of the CIDNP of the photosensitizing dye, 2,2′-dipyridyl. IET effects are not observed for mixtures of the amino acid or for the native state of lysozyme. The steady state CIDNP effects seen for denatured lysozyme thus depend not only on the accessibility of the amino acid residues on the surface of the protein but also on the reactivity of the radical intermediates.     

Vibrational control of molecular electron transfer reactions

ABSTRACT

Vibrational motions promote molecular electron transfer (ET) reactions by bringing electron donor and electron acceptor electronic states to fleeting resonance, and by modulating the donor-to-acceptor electronic coupling. The main experimental signature of molecular motion effects on the ET rate is the temperature dependence of the rate, which gives information about the overall free energy activation barrier for the ET reaction. Another approach to probing the vibrational control of ET reactions is to excite specific electron-transfer-active vibrational motions by external infrared (IR) fields. This type of experimental probe is potentially more specific than thermal excitation and recent experiments have shown that molecular ET rates can be perturbed by mode-specific IR driving. We review the theory and experiments of vibrational control of ET rates, and discuss future challenges that need to be tackled in order to achieve the mode-specific tuning of rates.     

Laser pulse control of ultrafast electron transfer reactions

The optimal control (OC) scheme for molecular dynamics is applied to the study of ultrafast bridge mediated electron transfer (ET). Utilizing the methods of dissipative quantum dynamics in combination with the OC approach the guided charge motion in a donor-bridge-acceptor system including a single active vibrational coordinate is studied. The control field drives the optical transition from the electronic ground-state of the ET system into the donor-level and can be used to prepare special electronic and vibrational states. In particular, it is demonstrated that charge localization becomes possible at the acceptor or bridge molecule as well as in the electronic ground-state of the ET system. Received 30 August 2000 and Received in final form 25 October 2000     

9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions

The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume. Copyright ? 2012 John Wiley & Sons, Ltd.     

A simple interpretation of anomalous angular distributions in heavy-ion induced two-step transfer reactions

A simple and transparent explanation is given of why CCBA calculations can fit simultaneously the normal as well as the anomalous angular distributions in transfer reactions between heavy ions.     

A class of collision processes with memory and application to simple chemical reactions in a solvent

We apply the general formalism of a class of non-Markovian processes which we have studied elsewhere to three simple models of chemical reactions: dissociation, isomerization, and diffusion in a double-well potential. Our method leads to explicitly solvable models and numerical computations. The results are in agreement with numerical simulation and stochastic dynamics studies of other authors.     

Dynamics of inner- and outer-sphere electron transfer in a polar solvent

In this paper, inner-sphere electron transfer reactions in a solvent are studied in the framework of multidimensional transition state theory. It is demonstrated that the preexponential factor essentially depends upon the interaction with the inner-sphere vibrational mode, increasing the rate of electron transfer as much as one order of magnitude. The prefactor is shown to be strongly dependent on the frequency of this vibration. At high frequencies the rate constant increases with the reorganization energy of this inner-sphere mode while at small frequencies, electron transfer is inhibited. Estimations of inner mode reorganization energies have been performed for system where it is necessary to account nonequilibrium solvent relaxation. Finally it is shown that the equilibrium approximation fails when the reaction is close to an activationless regime.     

A simple model for SmS

A simple model based on the resonant scattering theory can explain the first-order semiconductor-to-metal transition accompanied by a change of valency in SmS.     

Diffraction model study of two-nucleon transfer reactions

A simple diffraction model using sharp cut-off in the angular momentum space is adopted for the two-nucleon transfer reactions. Some (p,t) reactions on 1p shell nuclei are analysed with satisfactory results. The finite range calculations are performable in the model and they are compared with the results of approximate theories. The angular distributions in various theories differ little and the ratios of absolute magnitudes remain relatively constant.     

On the validity of marcus relationship for dissociative electron transfer reactions in solution

In this paper Monte Carlo simulations of a dissociative electron transfer reaction in solution have been performed in order to test to what extent the deviation of Marcus' relationship for this kind of reactions can be attributed to the features of the solute internal potential energy. It is shown that Marcus' equation does not apply to this kind of dissociative electron transfer processes if the ab initio solute internal potential energies are used. Conversely, if a Morse curve and its repulsive part are employed to describe the solute internal potential energies, Marcus' relationship is recovered. Then, the problem is reduced to what extent the ab initio solute internal potential energies can be represented by Morse curves.     

Reaction-yield-detected magnetic resonance in the intra-and intermolecular electron transfer reactions

The spin dynamics of the intermediate radical ion pairs formed in the intra-and intermolecular electron transfer reactions between N,N-dimethylaniline and phenanthrene is studied by employing the polymethylene-linked and nonlinked systems. Reaction-yield-detected magnetic resonance (RYDMR) experiments are performed by monitoring the exciplex fluorescence. From the theoretical consideration of the data, we conclude that the lifetime of the radical ion pair in the linked system is shorter than that in the nonlinked system. This tendency is opposite to what is generally observed in linked and nonlinked neutral biradical.     

A simple model for metamagnetic percolation

An Ising model with both antiferromagnetic and randomly diluted, infinitely strong ferromagnetic interactions is studied on a Bethe lattice. The results are used to interpret recent experimental data on the phase diagram of Fe_xMg_1-xCl₂.     

A simple model for radiation damping

Increasing interest has been shown in the method of matched asymptotic expansions for the construction and solution of the equations of motion in general relativity. This paper discusses a simple model which can, in principle, be solved exactly. A comparison of the two solutions shows that the matched asymptotic expansion technique determines correctly the final damping rate and frequency (at least to fourth order in a small parameter), but the phase information is spurious.     

A simple mathematical model for TTS

Published data on Temporary Threshold Shift (TTS) suggest that in many cases the rms pressure at threshold during and after exposure to noise varies in a simple exponential manner, and that the ultimate shift of pressure threshold for exposure to steady noise is dependent on the mean square pressure of that noise. This response could occur if some part of the hearing mechanism were heated by exposure to noise and were at the same time subject to Newtonian cooling, and if the change in the pressure threshold were proportional to the change of temperature. This model can explain the shapes of many growth and recovery curves given in dB, why time constants found for recovery from TTS appear greater than those for growth and why threshold shifts on ears with elevated thresholds appear smaller than those for ears with low thresholds. Because of individual variation, averaged dB results mask the nature of the processes involved. Hence, for a better understanding of TTS, individual ears should be studied separately, and, if possible, measurements should be made in rms Pa instead of dB.     

A simple model for diffuse reflection

Diffuse reflection from a matte nonabsorbing inhomogeneous medium such as white paint or paper can be described by a simple model in which light rays enter the volume of medium and then undergo a random walk until they reemerge from the surface. Lambert's law of diffuse reflection is an immediate consequence of the random walk. Another consequence of the volume interaction is that the light emerges from a different point than where it enters. This spreading of the light was measured for BaSO₄ white reflectance paint and for several kinds of paper. The random walk model implies a diffusion equation which makes predictions that are in reasonable agreement with the experiments. The spreading is proportional to an interaction length which, in this model, represents the range of distances that light rays penetrate before beginning their random walk.     

A simple model for surface relaxations

A simple model for surface relaxations is developed based on short-ranged two-body forces and a pressure applied to a crystal surface. Interplanar displacements are calculated as an elastic response to unresolved surface stresses which arise during the creation of the surface. For α-iron, the first-neighbor force is dominant at the surface and is significantly stronger than in the bulk, and surface pressure is stronger than the bulk Cauchy pressure and acts primarily on the outermost plane of atoms.