Modeling Gas-Phase Unimolecular Dissociation for Bond Dissociation Energies: Comparison of Statistical Rate Models within RRKM Theory.

The Rice-Ramsperger-Kassel-Marcus (RRKM) theory provides a simple yet powerful rate theory for calculating microcanonical rate constants. In particular, it has found widespread use in combination with gas-phase kinetic experiments of unimolecular dissociations to extract experimental bond dissociation energies (BDEs). We have previously found several discrepancies between the computed BDE values and the respective experimental ones, obtained with our empirical rate model, named L-CID. To investigate the reliability of our rate model, we conducted a theoretical analysis and comparison of the performance of conventional rate models and L-CID within the RRKM framework. Using the previously published microcanonical rate data as well as reaction cross-section data, we show that the BDE values obtained with the L-CID model agree with the ones from the other rate models within the expected uncertainty bounds. Based on this agreement, we discuss the possible rationalization of the good performance of the L-CID model.