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The Effect of Hartree-Fock Exchange on Scaling Relations and Reaction Energetics for C–H Activation Catalysts

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Abstract

High-throughput computational catalyst studies are typically carried out using density functional theory (DFT) with a single, approximate exchange-correlation functional. In open shell transition metal complexes (TMCs) that are promising for challenging reactions (e.g., C–H activation), the predictive power of DFT has been challenged, and properties are known to be strongly dependent on the admixture of Hartree-Fock (HF) exchange. We carry out a large-scale study of the effect of HF exchange on the predicted catalytic properties of over 1200 mid-row (i.e., Cr, Mn, Fe, Co) 3d TMCs for direct methane-to-methanol conversion. Reaction energy sensitivities across this set depend both on the catalytic rearrangement and ligand chemistry of the catalyst. These differences in sensitivities change both the absolute energetics predicted for a catalyst and its relative performance. Previous observations of the poor performance of global linear free energy relationships (LFERs) hold with both semi-local DFT widely employed in heterogeneous catalysis and hybrid DFT. Narrower metal/oxidation/spin-state specific LFERs perform better and are less sensitive to HF exchange than absolute reaction energetics, except in the case of some intermediate/high-spin states. Importantly, the interplay between spin-state dependent reaction energetics and exchange effects on spin-state ordering means that the choice of DFT functional strongly influences whether the minimum energy pathway is spin-conserved. Despite these caveats, LFERs involving catalysts that can be expected to have closed shell intermediates and low-spin ground states retain significant predictive power.

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Data Availability

The data sets and codes generated during and/or analyzed during the current study are available in the “methane-to-methanol reaction energy sensitivities” repository, at https://doi.org/10.5281/zenodo.4895418. The codes used in this work are also added to molSimplify.

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Acknowledgements

The authors acknowledge primary support for the catalyst design screen by the National Science Foundation under Grant numbers CBET-1704266 and CBET-1846426. A.N. was partially supported by a National Science Foundation Graduate Research Fellowship under Grant #1122374. Initial conception and data set generation for this study was supported by the Department of Energy under Grant number DE-SC0012702. Algorithm and workflow development as well as data collection strategies were supported by the Office of Naval Research under Grant numbers N00014-17-1-2956, N00014-18-1-2434, and N00014-20-1-2150. This work was carried out in part using computational resources from the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant number ACI-1548562. H.J.K. holds a Career Award at the Scientific Interface from the Burroughs Wellcome Fund, an AAAS Marion Milligan Mason Award, and an Alfred P. Sloan Fellowship in Chemistry, which supported this work.

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  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA

    Vyshnavi Vennelakanti, Aditya Nandy & Heather J. Kulik

  2. Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, 02139, USA

    Vyshnavi Vennelakanti & Aditya Nandy

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  1. Vyshnavi Vennelakanti
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All authors contributed to the study conception and design. Data collection and analysis were performed by VV and AN. The first draft of the manuscript was written by VV, revised by HJK, and all authors commented on and revised versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Heather J. Kulik.

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Vennelakanti, V., Nandy, A. & Kulik, H.J. The Effect of Hartree-Fock Exchange on Scaling Relations and Reaction Energetics for C–H Activation Catalysts. Top Catal 65, 296–311 (2022). https://doi.org/10.1007/s11244-021-01482-5

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