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. Employing a hybrid quantum mechanics/molecular mechanics approach with explicit solvent modeling, we compute kinetic rate constants that better match experimental measurements compared to previous gas-phase calculations. This methodology presents promising potential for accurately predicting kinetic rate constants in liquid-phase polymerization and depolymerization processes.
Unveiling Solvent Effects on β-Scissions through Metadynamics and Mean Force Integration
Serse, Francesco;Pelucchi, Matteo
2024-01-01
Abstract
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. Employing a hybrid quantum mechanics/molecular mechanics approach with explicit solvent modeling, we compute kinetic rate constants that better match experimental measurements compared to previous gas-phase calculations. This methodology presents promising potential for accurately predicting kinetic rate constants in liquid-phase polymerization and depolymerization processes.File | Dimensione | Formato | |
---|---|---|---|
serse-et-al-2024-unveiling-solvent-effects-on-β-scissions-through-metadynamics-and-mean-force-integration.pdf
Accesso riservato
Descrizione: articolo principale
:
Publisher’s version
Dimensione
3.73 MB
Formato
Adobe PDF
|
3.73 MB | Adobe PDF | Visualizza/Apri |
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.