Benchmarking of Density Functionals for Z-Azoarene Half-Lives via Automated Transition State Search

Abstract

Molecular photoswitches use light to interconvert from a thermodynamically stable isomer into a metastable isomer. Photoswitches have been used in photopharmacology, catalysis, and molecular solar thermal (MOST) materials because of their spatiotemporal activation. Visible-light-absorbing photoswitches are especially attractive because low-energy light minimizes undesired photochemical reactions and enables biological applications. Ideal photoswitches require well-separated absorption spectra for both isomers and long-lived metastable states. However, predicting thermal half-lives with density functional theory is difficult because it requires locating transition structures and chosing an accurate model chemistry. We now report EZ-TS; by automatically calculating activation energies for the thermal Z → E isomerization. We used 28 density functionals [local spin density approximation, generalized gradient approximation, meta-GGA, hybrid GGA, and hybrid meta-GGA] and five basis sets [6-31G(d), 6-31+G(d,p), 6-311+G(d,p), cc-pVDZ, and aug-cc-pVDZ]. The hybrid GGA functionals performed the best among all tested functionals. We demonstrate that the mean absolute errors of 14 model chemistries approach chemical accuracy.