Quantum Monte Carlo calculation of the bridge reaction barrier to hydrogen dissociation on Pt(111) (1705.08347v1)

Abstract: The yardstick of new first-principles approaches to key points on reaction paths at metal surfaces is chemical accuracy compared to reliable experiment. By this we mean that such values as the activation barrier are required to within 1 kcal/mol. Quantum Monte Carlo (QMC) is a promising (albeit lengthy) first-principles method for this and we are now beyond the dawn of QMC benchmarks for these systems, since hydrogen dissociation on Cu(111) has been studied with quite adequate accuracy in two improving QMC studies Hoggan ArXiv 2015, K. Doblhoff-Deir et al JCTC (2017). Pt and Cu require the use of pseudo-potentials in these calculations and we show that those of Pt are less problematic than those for Cu, particularly for QMC work. In this letter, we determine the activation barrier to hydrogen dissociation on Pt(111) using the bridging geometry. This is found to agree to better than chemical accuracy with recent Specific Reaction Parameter (SRP-DFT) work, which is itself within chemical accuracy of measurement (Kroes et al Cplett 2017). The results suggest the dissociation barrier for hydrogen on Pt(111) is close to 5.4 (QMC) and 6.2 (SRP-DFT) kcal/mol with a QMC standard error of 1.08 kcal/mol. This is encouraging for establishing less well-known benchmark values of industrial reaction barriers on Pt(111).