Pericyclic reaction benchmarks: hierarchical computations targeting CCSDT(Q)/CBS and analysis of DFT performance

Pascal Vermeeren, Marco Dalla Tiezza, Mark E. Wolf, Mitchell E. Lahm, Wesley D. Allen*, Henry F. Schaefer, Trevor A. Hamlin, F. Matthias Bickelhaupt

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Hierarchical, convergent ab initio benchmark computations were performed followed by a systematic analysis of DFT performance for five pericyclic reactions comprising Diels-Alder, 1,3-dipolar cycloaddition, electrocyclic rearrangement, sigmatropic rearrangement, and double group transfer prototypes. Focal point analyses (FPA) extrapolating to the ab initio limit were executed via explicit quantum chemical computations with electron correlation treatments through CCSDT(Q) and correlation-consistent Gaussian basis sets up to aug′-cc-pV5Z. Optimized geometric structures and vibrational frequencies of all stationary points were obtained at the CCSD(T)/cc-pVTZ level of theory. The FPA reaction barriers and energies exhibit convergence to within a few tenths of a kcal mol−1. The FPA benchmarks were used to evaluate the performance of 60 density functionals (eight dispersion-corrected), covering the local-density approximation (LDA), generalized gradient approximations (GGAs), meta-GGAs, hybrids, meta-hybrids, double-hybrids, and range-separated hybrids. The meta-hybrid M06-2X functional provided the best overall performance [mean absolute error (MAE) of 1.1 kcal mol−1] followed closely by the double-hybrids B2K-PLYP, mPW2K-PLYP, and revDSD-PBEP86 [MAE of 1.4-1.5 kcal mol−1]. The regularly used GGA functional BP86 gave a higher MAE of 5.8 kcal mol−1, but it qualitatively described the trends in reaction barriers and energies. Importantly, we established that accurate yet efficient meta-hybrid or double-hybrid DFT potential energy surfaces can be acquired based on geometries from the computationally efficient and robust BP86/DZP level.

Original languageEnglish
Pages (from-to)18028-18042
Number of pages15
JournalPhysical Chemistry Chemical Physics
Volume24
Issue number30
Early online date21 Jul 2022
DOIs
Publication statusPublished - 14 Aug 2022

Bibliographical note

Funding Information:
P. V., M. D. T., T. A. H., and F. M. B. thank the Netherlands Organization for Scientific Research (NWO) and the Dutch Astrochemistry Network (DAN) for financially supporting our work that has been carried out on the Dutch national e-infrastructure with the support of SURF Cooperative. Furthermore, this work was supported by the U.S. Department of Energy, Basic Energy Sciences, Chemical Sciences Division, Computational and Theoretical Chemistry (CTC), Grants DE-SC0018412 and DE-SC0018164.

Publisher Copyright:
© 2022 The Royal Society of Chemistry

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