Application of unimolecular reaction rate theory for highly flexible transition states to the dissociation of CH2CO into CH2 and CO

Abstract

A previously described implementation of Rice–Ramsberger–Kassel–Marcus (RRKM) theory for unimolecular dissociation processes involving a highly flexible transition state is applied to the dissociation of CH2CO into CH2 and CO. Results of theoretical calculations for the energy and angular momentum resolved rate constants are presented. Using an added dynamical approximation, the product vibrational–rotational distributions are also calculated. The calculated rate constants are compared with the corresponding experimentally determined quantities where possible. Comparison is also made with phase space theory (PST). The RRKM-based calculations are in good agreement with both the experimentally determined rate constants of Zewail and co-workers and the experimentally determined photofragment excitation spectra of Moore and co-workers. The results on rates are in contrast to the corresponding results from PST calculations. The RRKM-based theory for the product vibrational–rotational distributions predicts a moderately greater probability for vibrational excitations than does PST (particularly for excess energies just above the threshold for excitation of a particular vibrational mode of the products). In other respects the RRKM-based predictions of the ro-vibrational product state distributions are quite similar to those of PST.