First-principles prediction of absolute catalytic turnover frequencies
In plain words
Computer models can rank catalysts by trends, but they rarely predict the actual speed of a catalytic reaction. Small errors in computed energies change the predicted speed enormously.
Precise statement
For benchmark heterogeneous reactions (NH3 synthesis on Ru(0001) step sites, CO oxidation on Pt(111), methanol synthesis on Cu/ZnO), predict the absolute turnover frequency under specified temperature and pressure within a factor of 10 from first-principles energetics and kinetic modeling with no fitted parameters. An answer is a protocol (electronic structure accuracy, treatment of coverage, entropy and site heterogeneity) meeting this target on several reactions.
What would settle it
Blind comparison of computed turnover frequencies with measurements on well-characterized single-crystal or model catalysts.
Status in the literature
A 2005 first-principles microkinetic model of NH3 synthesis on Ru nanoparticles (Honkala et al., Science, https://doi.org/10.1126/science.1106435) matched measured rates to within about an order of magnitude, possibly helped by error cancellation; agreement across several reactions with controlled electronic-structure error is not established.