Serse, Francesco;
Bjola, Antoniu;
Salvalaglio, Matteo;
Pelucchi, Matteo;
(2024)
Unveiling Solvent Effects on β-Scissions through Metadynamics and Mean Force Integration.
Journal of Chemical Theory and Computation
, 20
(14)
pp. 6253-6262.
10.1021/acs.jctc.4c00383.
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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.
| Type: | Article |
|---|---|
| Title: | Unveiling Solvent Effects on β-Scissions through Metadynamics and Mean Force Integration |
| Location: | United States |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acs.jctc.4c00383 |
| Publisher version: | https://doi.org/10.1021/acs.jctc.4c00383 |
| Language: | English |
| Additional information: | Copyright © 2024 American Chemical Society. This publication is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/). |
| Keywords: | Computer Simulations, Free Energy, Kinetic Parameters, Solvents, Vacuum |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10194608 |
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