title: Perspective on the reactions between F- and CH3CH2F: the free energy landscape of the E2 and SN2 reaction channels.
abstract: Recently, we computed the 3D free energy surface of the base-induced elimination reaction between F(-) and CH(3)CH(2)F by using a powerful technique within Car-Parrinello molecular dynamics simulation. Here, the set of three order parameters is expanded to six, which allows the study of the competing elimination and substitution reactions simultaneously. The power of the method is exemplified by the exploration of the six-dimensional free energy landscape, sampling, and mapping out the eight stable states as well as the connecting bottlenecks. The free energy profile and barrier along the E2 and S(N)2 reaction channels are refined by using umbrella sampling. The two mechanisms do not share a common "E2C-like" transition state. Comparison with the zero temperature profiles shows a particularly significant entropy contribution to the S(N)2 channel.
authors.affiliation: Center for Molecular Modeling and Department of Chemistry, 231 South 34th Street, University of Pennsylvania, Philadelphia, PA 19104-6323, USA. ensing@cmm.upenn.edu
authors.forename: Bernd
authors.initials: B
authors.lastname: Ensing
authors.forename: Michael L
authors.initials: ML
authors.lastname: Klein
mesh_terms: D000465:Algorithms; D002384:Catalysis; D002627:Chemistry, Physical / Q000379:methods*; D019277:Entropy; D005459:Fluorides / Q000737:chemistry; D005461:Fluorine / Q000737:chemistry; D007477:Ions; D007700:Kinetics; D008956:Models, Chemical; D008968:Molecular Conformation; D016011:Normal Distribution; D012984:Software; D013696:Temperature; D013816:Thermodynamics; D013997:Time Factors
chemical_list: D007477:Ions; D005461:Fluorine; D005459:Fluorides