Computational aspects of Laplace transform inversion of thermal unimolecular rate constant

✍ Scribed by Christian Schoenenberger; Wendell Forst

• Book ID: 102880639
• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 654 KB
• Volume: 6
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.540060514

✦ Synopsis

The thermal limiting high-pressure unimolecular rate constant k , represents, operationally, the Laplace transform of the product of microcanonical rate constant for decomposition of molecules having specified energy E [k(E)] and the density of states [N(E)]. By inversion, it is possible to recover k(E)N(E), from which one can obtain the energy dependence of k(E) and the pressure dependence of k,,,, the thermal general-pressure unimolecular rate constant. This article examines numerical aspects of three methods of inversion, their reliability and dependence on sampling, i.e., on the number of available experimental data points, by comparing exact k(E) and kuni with those obtained by inversion. It turns out that the method of steepest descents is the best all-round performer.