First-principles prediction of absolute catalytic turnover frequencies · revision history

Revision 2

Accepted · core change · record

Changes against revision 1:

Title
First-principles prediction of absolute catalytic turnover frequencies
Plain
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 · changed · core
Revision 1: 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.
Revision 2: For benchmark heterogeneous reactions ($\mathrm{NH_3}$ 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.
Settled by
Blind comparison of computed turnover frequencies with measurements on well-characterized single-crystal or model catalysts.
Kind
well-posed
Answer type
value
References
(empty)
Literature status
open
Status note · changed
Revision 1: 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.
Revision 2: A 2005 first-principles microkinetic model of $\mathrm{NH_3}$ 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.
Posed since
(empty)

Decisions