The influence of DFT functional on catalysis

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.

Check out our recent invited paper in a special issue of Topics in Catalysis edited by Odile Eisenstein and Sason Shaik here!

About Us

The Kulik group focuses on the development and application of new electronic structure methods and atomistic simulations tools in the broad area of catalysis.

Our Interests

We are interested in transition metal chemistry, with applications from biological systems (i.e. enzymes) to nonbiological applications in surface science and molecular catalysis.

Our Focus

A key focus of our group is to understand mechanistic features of complex catalysts and to facilitate and develop tools for computationally driven design.

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