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Quantum effects in thermal reaction rates at metal surfaces

There is wide interest in developing accurate theories for predicting rates of chemical reactions that occur at metal surfaces, especially for applications in industrial catalysis. Conventional methods contain many approximations that lack experimental validation. In practice, there are few reactions where sufficiently accurate experimental data exist to even allow meaningful comparisons to theory. Here, we present experimentally derived thermal rate constants for hydrogen atom recombination on platinum single-crystal surfaces, which are accurate enough to test established theoretical approximations. A quantum rate model is also presented, making possible a direct evaluation of the accuracy of commonly used approximations to adsorbate entropy. We find that neglecting the wave nature of adsorbed hydrogen atoms and their electronic spin degeneracy leads to a 10× to 1000× overestimation of the rate constant for temperatures relevant to heterogeneous catalysis. These quantum effects are also found to be important for nanoparticle catalysts. Description Making surface chemistry more exact Accurate description of elementary steps of chemical reactions at surfaces is a long-standing challenge because of the lack of reliable experimental measurements of the corresponding rate constants, which also makes it impossible to rigorously validate theoretical estimates. Even for reactions as simple as thermal recombination of hydrogen atoms on platinum surfaces, previous experimental rate constants have only been obtained with large uncertainties. Using velocity-resolved kinetics and ion imaging–based calibration of absolute molecular beam fluxes, Borodin et al. managed to overcome established experimental difficulties and report unprecedentedly accurate rate constants for this reaction over a wide temperature range. They also demonstrate a parameter-free model that quantitatively reproduces the experiment, opening up new vistas for the growing field of computational heterogeneous catalysis. —YS Surface reaction rate constants were measured accurately so that a meaningful comparison with theory can now be made.