Site-Averaged Ab Initio Kinetics: Importance Learning for Multistep Reactions on Amorphous Supports

AS Zadeh and SA Khan and C Vandervelden and B Peters, JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 19, 2873-2886 (2023).

DOI: 10.1021/acs.jctc.3c00160

Single-atom centers on amorphous supports include catalysts for polymerization, partial oxidation, metathesis, hydrogenolysis, and more. The disordered environment makes each site different, and the kinetics exponentially magnifies these differences to make ab initio site- averaged kinetics calculations extremely difficult. This work extends the importance learning algorithm for efficient and precise site- averaged kinetics estimates to ab initio calculations and multistep reaction mechanisms. Specifically, we calculate site-averaged proton transfer relaxation rates on an ensemble of cluster models representing Bronsted acid sites on silica-alumina. We include direct and water- assisted proton transfer pathways and simultaneously estimate the water adsorption and activation enthalpies for forward and backward proton transfers. We use density functional theory (DFT) to obtain a site- averaged rate, somewhat like a turnover frequency, for the proton transfer relaxation rate. Finally, we show that importance learning can provide orders-of-magnitude acceleration over standard sampling methods for site-averaged rate calculations in cases where the rate is dominated by a few highly active sites.

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