ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
2 files

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

preprint
submitted on 17.02.2021, 16:55 and posted on 18.02.2021, 12:50 by Daniel Adrion, Danil Kaliakin, Patrick Neal, Steven Lopez
Molecular photoswitches use light to interconvert from a thermodynamically stable isomer into a meta-stable isomer. Chemists and materials scientists have applied photoswitches in photopharmacology, catalysis, and molecular solar thermal (MOST) materials. Visible-light-absorbing photoswitches are attractive because the relatively low-energy light minimizes undesired photochemical reactions and enables biological applications. Designing ideal photoswitches requires long-lived metastable states; predicting their half-lives with theory is difficult because it requires locating transition structures. We now report the EZ-TS code, which automates the prediction of rate constants for the thermal Z → E isomerization. We leverage EZ-TS to automate the location of the favored transition structure and to comprehensively benchmark the performance of 140 model chemistries against the experimental rate constants of 11 azoarenes. We used 28 density functionals [local spin density approximation, generalized gradient approximation, meta-GGA, hybrid GGA, 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 of all tested functional classes. We demonstrate that the mean absolute errors of 14 model chemistries approach chemical accuracy, and mPWPW91/6-31+G(d,p) achieves chemical accuracy and should be used with EZ-TS.

Funding

NSF-OAC-1940307

ONR-N00014-12-1-0828

History

Email Address of Submitting Author

adrion.d@northeastern.edu

Institution

Northeastern University

Country

United States of America

ORCID For Submitting Author

0000-0002-0126-2956

Declaration of Conflict of Interest

The authors declare no conflict of interest

Version Notes

This is the first submission to an ACS Journal.

Exports