Atomistic dynamics of elimination and nucleophilic substitution disentangled for the F- + CH3CH2Cl reaction

Chemical reaction dynamics are studied to monitor and understand the concerted motion of several atoms while they rearrange from reactants to products. When the number of atoms involved increases, the number of pathways, transition states and product channels also increases and rapidly presents a challenge to experiment and theory. Here we disentangle the dynamics of the competition between bimolecular nucleophilic substitution (S(N)2) and base-induced elimination (E2) in the polyatomic reaction F- + CH3CH2Cl. We find quantitative agreement for the energy- and angle-differential reactive scattering cross-sections between ion-imaging experiments and quasi-classical trajectory simulations on a 21-dimensional potential energy hypersurface. The anti-E2 pathway is most important, but the S(N)2 pathway becomes more relevant as the collision energy is increased. In both cases the reaction is dominated by direct dynamics. Our study presents atomic-level dynamics of a major benchmark reaction in physical organic chemistry, thereby pushing the number of atoms for detailed reaction dynamics studies to a size that allows applications in many areas of complex chemical networks and environments. As the number of atoms involved in a reaction increases, so do the experimental and theoretical challenges faced when studying their dynamics. Now, using ion-imaging experiments and quasi-classical trajectory simulations, the dynamics of the polyatomic reaction F- + CH3CH2Cl have been studied and the competition between bimolecular nucleophilic substitution and base-induced elimination has been disentangled.

Automated summary

The dynamics of the polyatomic reaction F- + CH3CH2Cl have been studied using ion-imaging experiments and quasi-classical trajectory simulations. The anti-E2 pathway is found to be most important, but the relevance of the S(N)2 pathway increases with collision energy, with the reaction being dominated by direct dynamics.