Lindemann-Hinshelwood equation

This ensures the correct connection between the one-dimensional Kramers model in the regime of large friction and multidimensional unimolecular rate theory in that of low friction, where Kramers model is known to be incorrect as it is restricted to the energy diffusion limit. For low damping, equation (A3.6.29) reduces to the Lindemann-Hinshelwood expression, while in the case of very large damping, it attains the Smoluchowski limit... 

The expression for N t, E) in equation (A3.12.67) has been used to study [103.104] how the Porter-Thomas P k) affects the collision-averaged monoenergetic unimolecular rate constant k (Si, E) [105] and the Lindemann-Hinshelwood unimolecular rate constant T) [47]. The Porter-Thomas P k) makes k, E) pressure... 

Equation (2.11) can be considered as a switching function describing the transition of k from feo to k with a value of k = k /2 at the center of the fall-off curve. We call Eq. (2.11), which is based on the model for unimolecular reactions that was first given 50 years ago by Lindemann and Hinshelwood, the Lindemann-Hinshelwood expression. It is shown in Fig. 2. 

The correct treatment of the mechanism (equation (A3.4.25), equation (A3.4.26) and equation (A3.4.27), which goes back to Lindemann [18] and Hinshelwood [19], also describes the pressure dependence of the effective rate constant in the low-pressure limit ([M] < [CHoNC], see section A3.4.8.2). 

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