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Jason R. Green edited Kinetic model with dynamic disorder.tex
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\section{Second-order kinetic model with dynamical disorder}
The effects of dynamic disorder on higher ordered kinetics can be investigated through We adapt the Kohlrausch-Williams-Watts (KWW)
model. This expression takes model for stretched exponential decay to study the
expotential effect of dynamical disorder on higher-order kinetics. In first-order kinetics, stretched exponential decay
predicted by classical kinetics involves a two-parameter survival function and
stretches the curve through associated time-depedent rate coefficient. The parameters are a
time depedent characteristic rate
coefficient $\omega$ or inverse timescale, $\omega$, and
the coopertavity of decay $\beta$,
making it a conventient expression for interpreting which controls the degree dynamic disorder.
The use of this model is intended to be a proof of principle, however any system with a time depedent rate coefficient may be analyzed. Assuming an overall second order process with a time depedent rate coefficient the survival function is written as $S(t)=\frac{1}{1+(\omega t[A_0])^{\beta}}$.Thorugh the time derivitive of the inverse of the survival function the time depedent rate coefficient characterising the deacy is expressed as $k(t)=\frac{\beta([A_0]\omega t)^{\beta}}{t}$. We see this definition of the rate coefficient maintains a depedence on the initial concentration of the reactants which is a unique result when compared to first order kinetics, and propagates thorugh the remainder of the
calculations.Next calculations. Next the time depedent rate coefficient is integrated to determine the statistical length.
\begin{equation}
\mathcal{L}_{KWW}(\Delta{t})=[A_0\omega t]^{\beta}\bigg|_{t_i}^{t_f}
\end{equation}
To understand the effect of fluctuations on the rate coefficient we then integrate over the square, determining the divergence.
\begin{equation}
\mathcal{J}_{KWW}(\Delta{t}) =
\frac{\Delta t[A_0]^{2\beta}\beta^{2}\omega^{2\beta}t^{2\beta-1}}{2\beta-1}\bigg|_{t_i}^{t_f}
\end{equation}
This form shows the $\frac{1}{2}$ $\beta$ valuse must be evaluated seperately which yields the final result for comparison. And when $\beta=\frac{1}{2}$,
\begin{equation}
\mathcal{J}_{KWW}(\Delta{t})=\Delta \mathcal{J}_{KWW}(\Delta{t}) = \Delta t [A_0]\beta^2\omega^{2\beta} \ln(t)\bigg|_{t_i}^{t_f}
\end{equation}
We use of this model is intended to be a proof of principle, however any system with a time depedent rate coefficient may be analyzed.