Abstract
Accurate parameterization of theoretical unimolecular rate coefficients into simple analytical expressions is an important requirement for effective modeling of large chemical kinetic systems. Currently available parameterization schemes predict rate coefficients that could deviate from the “exact” theory by as much as a factor of two. It is suggested in this study to replace the Loretz-type pressure broadening of Troe's fall-off formula for unimolecular rate coefficients with a Gaussian form. Numerical tests were performed for several decomposition reactions over wide ranges of pressure and temperature using “rigid” RRKM calculations and solutions of master equations. The results demonstrate that the use of Gaussian broadening improves substantially the accuracy of Troe's formula.
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