The Laplace transformation approach-saddle point approximation method of very high accuracy and application to the calculation of density of vibrational states of molecules in unimolecular reaction kinetics. II - The calculation of the reaction rate const

Abstract

In the present paper rhe number of states and rhe density of vibrational states, obtained by Laplace transformation method saddle point approximation (in the previous paper), are used for calculating (by the aid of RRKM theory) the reaction rate constant of 1,1-dicloxiclopropan2,3-diclopropen isomerization. Results of this process give us all data for drawing the In(kuni/k∞)- InPcurve (the fall off curve). This way of investigation, in comparison with others ones (the direct count, Whitten - Rabinovitch methods) appears to have great advantage, because it does not coma in internal methodological contraditions and behaviour of the fall- off curve is in very good agreement with experiments