A Strategy for Modeling Nonstatistical Reactivity Effects: Combining Chemical Activation Estimates with a Vibrational Relaxation Model

The kinetics of many chemical reactions can be readily explained with a statistical approach, for example, using a form of transition state theory and comparing calculated Gibbs energies along the reaction coordinate(s). However, there are cases where this approach fails, notably when the vibrational relaxation of the molecule to its statistical equilibrium occurs on the same time scale as the reaction dynamics, whether it is caused by slow relaxation, a fast reaction, or both. These nonstatistical phenomena are then often explored computationally using (quasi)classical ab initio molecular dynamics by calculating a large number of trajectories while being prone to issues such as zero-point energy leakage. On the other side of the field, we see resource-intensive quantum dynamics simulations, which significantly limit the size of explorable systems. We find that using a Fermi’s golden rule type of model for vibrational relaxation, based on anharmonic coupling constants, we can extract the same qualitative information while giving insights into how to enhance (or destroy) the bottlenecks causing the phenomena. We present this model as a middle ground for exploring complex nonstatistical behavior, capable of treating medium-sized organic molecules or biologically relevant fragments. We also cover the challenges involved, in particular quantifying the excess energy in terms of vibrational modes. Relying on readily available electronic structure methods and providing results in a simple master equation form, this model shows promise as a screening tool for opportunities in mode-selective chemistry without external control.