Practical and accurate density functionals for transition-metal heterogeneous catalysis

TL;DR

This paper introduces new hybrid and double-hybrid density functionals specifically designed for transition-metal catalysis, achieving unprecedented accuracy in predicting adsorption energies and barrier heights, thus advancing computational catalyst design.

Contribution

The authors develop a systematic framework for creating highly accurate density functionals tailored to transition-metal surfaces, including the first double-hybrid functional reaching chemical accuracy for key catalytic properties.

Findings

Double-hybrid functional achieves transition-metal chemical accuracy on average.

Both functionals accurately predict key catalytic properties and correct standard functional failures.

Framework facilitates development of improved functionals for heterogeneous catalysis.

Abstract

Density functional theory (DFT) underpins modern atomistic simulations of transition-metal surfaces. It can predict key properties linked to catalytic performance, such as adsorption energies and barrier heights, enabling new paradigms in rational catalyst design. These applications require reliable density functionals, however achieving transition-metal chemical accuracy (13 kJ/mol) on these properties remains challenging. We introduce a framework for designing new functionals tailored to catalytic processes on transition-metal surfaces, building on recent non-self-consistent approaches. Within this framework, we develop a hybrid and a double-hybrid functional that achieve unprecedented accuracy, with the latter reaching transition-metal chemical accuracy on average across 39 experimental adsorption reactions. In addition, both functionals demonstrate balanced performance for 17 barrier heights and correct qualitative failures of standard functionals, including CO adsorption on Pt(111) and graphene on Ni(111). They are computationally efficient, readily integrated into existing DFT codes, and supported by open-source workflows to facilitate adoption. More broadly, this framework provides a systematic route towards improved functionals for heterogeneous catalysis and complex materials.