Bouncing off walls - widths of exit channels from shallow minima can dominate selectivity control

Mengna Bai; Zhitao Feng; Jun Li; Dean J Tantillo

doi:10.1039/d0sc04036c

Bouncing off walls - widths of exit channels from shallow minima can dominate selectivity control

Chem Sci. 2020 Aug 31;11(36):9937-9944. doi: 10.1039/d0sc04036c.

Authors

Mengna Bai^{1

2}, Zhitao Feng², Jun Li¹, Dean J Tantillo²

Affiliations

¹ School of Chemistry and Chemical Engineering, Chongqing Key Laboratory of Theoretical and Computational Chemistry, Chongqing University No. 55 Daxuecheng South Rd., Shapingba Chongqing 401331 China.
² Department of Chemistry, University of California Davis One Shields Avenue Davis CA 95616 USA djtantillo@ucdavis.edu.

Abstract

A selectivity model based on the widths of pathways to competing products, rather than barrier heights, is formulated for the butadiene + allyl cation reaction. This model was arrived at via analysis of stationary points, intrinsic reaction coordinates, potential energy surface shapes and direct dynamics trajectories, all determined using quantum chemical methods.