J Phys Chem B. 2016 Mar 03;120(8):1486-96. doi: 10.1021/acs.jpcb.5b06646. Epub 2015 Sep 01.

Comparison of Relative Activation Energies Obtained by Density Functional Theory and the Random Phase Approximation for Several Claisen Rearrangements.

The journal of physical chemistry. B

Madeline K Hartley, Seanna Vine, Elizabeth Walsh, Sara Avrantinis, G William Daub, Robert J Cave

PMID: 26308793 DOI: 10.1021/acs.jpcb.5b06646

Abstract

We investigate several representative density functional theory approaches for the calculation of relative activation energies and free energies of a set of model pericyclic reactions, some of which have been studied experimentally. In particular, we use a standard hybrid functional (B3LYP), the same hybrid functional augmented with a basis set superposition error and dispersion correction, a meta-hybrid functional developed to treat transition states and weak interactions (M06-2X), and the recently implemented random phase approximation (RPA) based on Kohn-Sham orbitals from conventional density functional theory by Furche and co-workers. We apply these methods to calculate relative activation energies and estimated free energies for the amide acetal Claisen rearrangement. We focus on relative activation energies to assess the effects of steric and weak interactions in the various methods and compare with experiment where possible. We also discuss the advantages of using this set of reactions as a test bed for the comparison of treatments of weak interactions. We conclude that all methods yield similar trends in relative reactivity, but the RPA yields results in best agreement with the experimental values.

Publication Types

• Journal Article
• Research Support, Non-U.S. Gov't