First principles assessment of solvent induced cage effects on intramolecular hydrogen transfer in the free radical polymerization of acrylates.

We investigate the rate constant of poly-butyl acrylate backbiting between 310 and 510 K using semi-empirical metadynamics in the gas phase, bulk and solution. The simulations in the condensed phase are performed through a hybrid quantum mechanics/molecular mechanics approach. The free energy landscape associated with the reactive events under vacuum and in the condensed phase is used to correct harmonic transition state theory (TST) rate constants.

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 to investigate solvent effects on chemical reaction kinetics. The newly developed methodology is applied to the β-scission of butyl acrylate (BA) dimer in polar (water) and nonpolar (xylene and BA monomer) solvents. The results show that solvation in both polar and nonpolar environments reduces the free energy barrier of activation by ∼4 kcal/mol and decreases the pre-exponential factor 2-fold.