Solvent dynamics rate constant

The role of solvent dynamics in the electron transfer reaction at a Pt electrode was discussed utilizing the theory of Zusman. In this work, ° the solvent-dependent rate constant for the electron transfer reaction at an electrode was given as... 

Experiments aimed at probing solvent dynamical effects in electrochemical kinetics, as in homogeneous electron transfer, are only of very recent origin, fueled in part by a renaissance of theoretical activity in condensed-phase reaction dynamics [47] (Sect. 3.3.1). It has been noted that solvent-dependent rate constants can sometimes be correlated with the medium viscosity, t] [101]. While such behavior may also signal the onset of diffusion-rather than electron-transfer control, if the latter circumstances prevail this finding suggests that the frequency factor is controlled by solvent dynamics since td and hence rL [eqn. (23), Sect. 3.3.1] is often roughly proportional to... 

Predicting the solvent or density dependence of rate constants by equation (A3.6.29) or equation (A3.6.31) requires the same ingredients as the calculation of TST rate constants plus an estimate of and a suitable model for the friction coefficient y and its density dependence. While in the framework of molecular dynamics simulations it may be worthwhile to numerically calculate friction coefficients from the average of the relevant time correlation fiinctions, for practical purposes in the analysis of kinetic data it is much more convenient and instructive to use experimentally detemiined macroscopic solvent parameters. 

Investigation of water motion in AOT reverse micelles determining the solvent correlation function, C i), was first reported by Sarkar et al. [29]. They obtained time-resolved fluorescence measurements of C480 in an AOT reverse micellar solution with time resolution of > 50 ps and observed solvent relaxation rates with time constants ranging from 1.7 to 12 ns. They also attributed these dynamical changes to relaxation processes of water molecules in various environments of the water pool. In a similar study investigating the deuterium isotope effect on solvent motion in AOT reverse micelles. Das et al. [37] reported that the solvation dynamics of D2O is 1.5 times slower than H2O motion. 

The development of comprehensive models for transition metal carbonyl photochemistry requires that three types of data be obtained. First, information on the dynamics of the photochemical event is needed. Which reactant electronic states are involved What is the role of radiationless transitions Second, what are the primary photoproducts Are they stable with respect to unimolecular decay Can the unsaturated species produced by photolysis be spectroscopically characterized in the absence of solvent Finally, we require thermochemical and kinetic data i.e. metal-ligand bond dissociation energies and association rate constants. We describe below how such data is being obtained in our laboratory. 

Esr spectroscopy has also been used to study pure solvent dynamics in electron self-exchange reactions (Grampp et al., 1990a Grampp and Jaenicke, 1984a,b). When the systems are not linked by a spacer (i.e. TCNQ- /TCNQ (TCNQ = tetracyanoquinodimethane), the homogeneous bimolecular rate constants /chom are given by (10), with fcA the association constant and kET... 

Rate constant for the exchange of a particular coordinated solvent molecule (6). By molecular dynamics method. 

The TST rate constant for electronically adiabatic ET reactions is the well-known Marcus rate constant kjjj [27-29], In the language of this chapter, solvent dynamical effects can alter the actual rate from this limit due to the friction influence. The corresponding GH equations for kct = / kfj are strictly analogous... 

This mechanism is supported by identical dissociation and racemization rate constants. This further implies either that the bis species M(AA)2 is racemic as formed, or that it may racemize (by a cis-trans change, or by a dissociative or intramolecular path) more rapidly than it re-forms iris in the dynamic equilibrium (7.23). Identical activation parameters for the dissociation (to the bis species) and racemization in aqueous acid (Table 7.5) and other solvents of Nifphen) " and Ni(bpy)3 indicate that these ions racemize by an intermolecular mechanism. This is the only such example for an M(phen)"+ or M(bpy) + species (see Table 7.5) although recently it has been observed that Fe(bps)3 (bps is the disulfonated phenanthroline ligand shown in 13, Chap. 1) but not Fe(phen)3+ also racemizes predominantly by a dissociative mechanism in water. For the other tr/s-phenanthroline complexes (and for Fe(bps)3 in MeOH rich, MeOH/HjO mixtures ) an intramolecular mechanism pertains since the racemization rate constant is larger than that for complete dissociation of one ligand, Table 7.5. 

The mechanistic importance of the study of the temperature dependence of the rate constants is very clearly indicated in the study of the dynamics of fluorenyllithium in diethyl ether (5 , 3) Although the values of the rate constants fitted rather well with the values expected for a diffusional assocation-dissociation process at one temperature, the dissociation rate constant decreased with increasing temperature. This is a definite proof for the intervention of a solvent-separated ion-pair in the dissociation pathway. 

The nature of the active species in the anionic polymerization of non-polar monomers, e. g. styrene, has been disclosed to a high degree. The kinetic measurements showed, that the polymerization proceeds in an ideal way, without side-reactions, and that the active species exist in the form of free ions, solvent-sparated and contact ion pairs, which are in a dynamic equilibrium (l -4). For these three species the rate constants and activation parameters (including the activation volumes), as well as the rate constants and equilibrium constants of interconversion have been determined (4-7.) Moreover, it could be shown by many different methods (e. g. conductivity and spectroscopic methods) that the concept of solvent-separated ion pairs can be applied to many ionic compounds in non-aqueous polar solvents (8). 

Since enzyme catalysis and regulation are dynamic processes, the dynamics of hydrogen bonding is also an important consideration. In relatively weakly hydrogen bonding solvents, such as the first four entries in Table I, the association rate is essentially diffusion controlled, whereas the association rate constants for the last two entries are considerably less than expected for a diffusion-controlled process. This can be understood... 

Chuang, Y.-Y., Radhakrishnan, M. L., Fast, P. L., Cramer, C. J., and Truhlar, D. G. 1999. Direct Dynamics for Free Radical Kinetics in Solution Solvent Effect on the Rate Constant for the Reaction of Methanol with Atomic Hydrogen ,. /. Phys. Chem. A, 103, 4893. 

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