Unveiling solvent effects on β-scissions through Metadynamics and Mean Force Integration

This study introduces a methodology that combines accelerated molecular dynamics and Mean Force Integration (MFI) to investigate solvent effects on chemical reaction kinetics. The newly developed methodology is applied to the $\beta$-scission of Butyl Acrylate (BA) dimer in polar (water) and non-polar (xylene, BA monomer) solvents. The results show that solvation in both polar and non-polar environments reduces the free energy barrier of activation by $\sim$ 4 [kcal/mol] and decreases the pre-exponential factor twofold. Employing a hybrid QM/MM approach with explicit solvent modelling, we compute kinetic rate constants that better match experimental measurements compared to gas-phase calculations. This methodology presents promising potential for accurately predicting kinetic rate constants in liquid-phase polymerization and depolymerization processes.