Enhancing Eyringpy: Accurate Rate Constants with Canonical Variational Transition State Theory and the Hindered Rotor Model

Abstract

The recrossing effect and hindered rotations can lead to significant inaccuracies in rate constant calculations using transition state theory and the harmonic oscillator approximation. To address these issues, we enhanced Eyringpy, a Python-based computational tool, by integrating the canonical variational transition state theory (CVT) and the hindered rotor model, effectively mitigating the limitations of traditional methods. CVT rate constants are calculated using electronic structure data from nonstationary points along the minimum-energy path. Additionally, we developed an algorithm based on reaction force analysis to autonomously select relevant nonstationary points. Torsions are modeled using one-dimensional hindered rotor approaches proposed by Pitzer-Gwinn and Ayala-Schlegel.