eprintid: 10194608 rev_number: 7 eprint_status: archive userid: 699 dir: disk0/10/19/46/08 datestamp: 2024-07-16 14:00:00 lastmod: 2024-07-16 14:00:00 status_changed: 2024-07-16 14:00:00 type: article metadata_visibility: show sword_depositor: 699 creators_name: Serse, Francesco creators_name: Bjola, Antoniu creators_name: Salvalaglio, Matteo creators_name: Pelucchi, Matteo title: Unveiling Solvent Effects on β-Scissions through Metadynamics and Mean Force Integration ispublished: inpress divisions: UCL divisions: B04 divisions: F43 note: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. 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. date: 2024-07-03 date_type: published publisher: American Chemical Society (ACS) official_url: http://10.0.103.66/chemrxiv-2024-rn2rz full_text_type: other language: eng verified: verified_manual elements_id: 2292104 doi: 10.1021/acs.jctc.4c00383 medium: Print-Electronic lyricists_name: Salvalaglio, Matteo lyricists_id: MSALV72 actors_name: Salvalaglio, Matteo actors_id: MSALV72 actors_role: owner funding_acknowledgements: EP/X033139/1 [UK Research and Innovation] full_text_status: restricted publication: Journal of Chemical Theory and Computation event_location: United States citation: 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 10.1021/acs.jctc.4c00383 <https://doi.org/10.1021/acs.jctc.4c00383>. (In press). document_url: https://discovery.ucl.ac.uk/id/eprint/10194608/1/paper_bscission_chemrxiv-2.pdf