Pressure-Dependent Rate Constant Predictions Utilizingthe Inverse Laplace Transform: A Victim of Deficient Input Data

摘要

k(E) can be calculated either from the Rice–Ramsperger–Kassel–Marcus theory or by inverting macroscopic rate constants k(T). Here, we elaborate the inverse Laplace transform approach for k(E) reconstruction by examining the impact of k(T) data fitting accuracy. For this approach, any inaccuracy in the reconstructed k(E) results from inaccurate/incomplete k(T) description. Therefore, we demonstrate how an improved mathematical description of k(T) data leads to accurate k(E) data. Refitting inaccurate/incomplete k(T), hence, allows for recapturing k(T) information that yields more accurate k(E) reconstructions. The present work suggests that accurate representation of experimental and theoretical k(T) data in a broad temperature range could be used to obtain k(T,p). Thus, purely temperature-dependent kinetic models could be converted into fully temperature- and pressure-dependent kinetic models.