Theory Grote-Hynes

CLASSICAL PARTICLE CHARGE TRANSFER-GROTE-HYNES THEORY... 

We begin by giving a brief account of Grote-Hynes Theory [1,2] for reaction rate constants. This theory has been verified for a very wide range of solution reactions via computer simulation [3-12] and has also proved useful in comparison... 

A cornerstone of condensed phase reaction theory is the Kramers-Grote-Hynes theory. In a seminal paper Kramers solved the Fokker-Plank equation in two limiting cases, for high and low friction, by assiuning Markovian dynamics y(t) 5(t). He foimd that the rate is a non-monotonic function of the friction ( Kramers turnover .) Further progress was made by Grote and Hynes - who... 

In the limit of very large viscosity, such as the one observed near the glass transition temperature, it is expected that rate of isomerization will ultimately go to zero. It is shown here that in this limit the barrier crossing dynamics itself becomes irrelevant and the Grote-Hynes theory continues to give a rate close to the transition theory result. However, there is no paradox or difficulty here. The existing theories already predict an interpolation scheme that can explain the crossover to inverse viscosity dependence of the rate... 

In Fig. 16, the values of the exponent a are plotted against the barrier frequency this is clearly a kind of master curve that summarizes the essence of much of the work reported here. When the rate is calculated from Grote-Hynes theory, this curve depends only weakly on temperature. 

Chapters 9-11 deal with elementary reactions in condensed phases. Chapter 9 is on the energetics of solvation and, for bimolecular reactions, the important interplay between diffusion and chemical reaction. Chapter 10 is on the calculation of reaction rates according to transition-state theory, including static solvent effects that are taken into account via the so-called potential-of-mean force. Finally, in Chapter 11, we describe how dynamical effects of the solvent may influence the rate constant, starting with Kramers theory and continuing with the more recent Grote-Hynes theory for... 

There are in principle dynamical recrossing corrections to the normal mode TST rate constant Equation (3.127) itself due to solvent frictional effects, which can be calculated via Grote-Hynes theory [81,82] when the time-dependent frictions on the three... 

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