2018/09/03 by GiovanniMaria Piccini, Piccini, GiovanniMaria, Dan Mendels +3 · 1 citation
Engineering · Physics and Astronomy · #Chemical Physics (physics.chem-ph) #Computational Physics (physics.comp-ph) #FOS: Physical sciences #Molecular Junctions and Nanostructures #Origins and Evolution of Life #Surface Chemistry and Catalysis
paper · pdf · doi:10.48550/arxiv.1809.00504
openalex publication_date 2018/09/03 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
We introduce an extension of a recently published method\citeMendels2018 to obtain low-dimensional collective variables for studying multiple states free energy processes in chemical reactions. The only information needed is a collection of simple statistics of the equilibrium properties of the reactants and product states. No information on the reaction mechanism has to be given. The method allows studying a large variety of chemical reactivity problems including multiple reaction pathways, isomerization, stereo- and regiospecificity. We applied the method to two fundamental organic chemical reactions. First we study the \ceSN2 nucleophilic substitution reaction of a \ceCl in \ceCH2 Cl2 leading to an understanding of the kinetic origin of the chirality inversion in such processes. Subsequently, we tackle the problem of regioselectivity in the hydrobromination of propene revealing that the nature of empirical observations such as the Markovinikov's rules lies in the chemical kinetics rather than the thermodynamic stability of the products.