Transition States Energies from Machine Learning: An Application to Reverse Water–Gas Shift on Single-Atom Alloys

Abstract

Obtaining accurate transition state (TS) energies is a bottleneck in computational screening of complex materials and reaction networks due to the high cost of TS search methods and ab initio methods such as density functional theory (DFT). Here, we propose a machine learning (ML) model for predicting TS energies based on Gaussian process regression with the Wasserstein Weisfeiler-Lehman graph kernel (WWL-GPR). Applying the model to predict adsorption and TS energies for the reverse water–gas shift (RWGS) reaction on single-atom alloy (SAA) catalysts, we show that it can significantly improve the accuracy compared to traditional approaches based on scaling relations or ML models without a graph representation. Further benefiting from the low cost of model training, we train an ensemble of WWL-GPR models to obtain uncertainties through subsampling of the training data and show how these uncertainties propagate to turnover frequency (TOF) predictions through the construction of an ensemble of microkinetic models. Comparing the errors in model-based vs DFT-based TOF predictions, we show that the WWL-GPR model reduces errors by almost an order of magnitude compared to scaling relations. This demonstrates the critical impact of accurate energy predictions on catalytic activity estimation. Finally, we apply our model to screen other materials, identifying promising catalysts for RWGS. This work highlights the power of combining advanced ML techniques with DFT and microkinetic modeling for screening catalysts for complex reactions like RWGS, providing a robust framework for future catalyst design.