Heterogeneous catalyst surfaces are dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts’ action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the timescales of the dynamic changes. Here we use the CO oxidation reaction and a Pd(100) model catalyst to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. A key finding is that at 3.2 mbar total pressure a metallic, predominantly CO-covered metallic surface turns highly active for a few seconds once the O2:CO ratio becomes high enough to lift the CO poisoning effect before mass transport limitations triggers formation of a √5 oxide.

We present an analysis of the dispersion interaction energy and forces in density-functional theory from the point of view of the adiabatic connection between the Kohn-Sham non-interacting and fully interacting systems. Accurate coupled-cluster singles-doubles-perturbative-triples [CCSD(T)] densities are computed for the helium dimer and used to construct the exchange-correlation potential of Kohn-Sham theory, showing agreement with earlier results presented for the Hartree-Fock-Kohn-Sham method [M. Allen and D. J. Tozer, J. Chem. Phys. 117, 11113 (2002)]. The accuracy of the methodology utilized to determine these solutions is checked by calculation of the Hellmann-Feynman forces based on the Kohn-Sham densities, which are compared with analytic CCSD(T) forces. To ensure that this comparison is valid in a finite atomic-orbital basis set, we employ floating Gaussian basis functions throughout and all results are counterpoise corrected. The subtle charge-rearrangement effects associated with the dispersion interaction are highlighted as the origin of a large part of the dispersion force. To recover the exchange-correlation components of the interaction energy, adiabatic connections are constructed for the supermolecular system and for its constituent atoms; subtraction of the resulting adiabatic-connection curves followed by integration over the interaction strength recovers the exchange-correlation contribution relevant to the density-functional description of the dispersion interaction. The results emphasize the long-ranged, dynamically correlated nature of the dispersion interaction between closed-shell species. An alternative adiabatic-connection path is also explored, where the electronic interactions are introduced in a manner that emphasizes the range of the electronic interactions, highlighting their purely long-ranged nature, consistent with the success of range-separated hybrid approaches in this context.

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19The CO oxidation behavior under excess oxygen and near stoichiometric conditions over the surface 20 of Pd3Au(100) has been studied by combining near-ambient pressure X-ray photoelectron 21 spectroscopy and quadrupole mass spectrometry and compared to Pd(100). During heating and 22 cooling cycles, normal hysteresis in the CO2 production, i.e. with the light-off temperature being 23 higher than the extinction temperature, is observed for both surfaces. On both Pd3Au(100) and 24Pd(100) the (√5x√5)R27° surface oxide structure is present during CO2 production under excess 25 oxygen conditions (O2:CO = 10:1), while at near stoichiometric conditions (O2:CO = 1:1) the surfaces 26 are covered with atomic oxygen. Au as alloying element hence induces only minor differences in the 27 observed hysteresis and the active phase compared to pure Pd. Alloying with Au thus yields a 28 different behavior compared to Ag, where reversed hysteresis is observed for CO2 production over 29 Pd75Ag25(100) at similar conditions [Fernandes et al., ACS Catal. (2016)

Highlights-H2 dissociation on Co is promoted by undercoordinated sites -But hydrogen atoms bind less strongly there compared to flat terrace sites -In FTS steps and kinks may be the dominant source of surface hydrogen atoms

Heterogeneous catalyst surfaces are highly dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts’ action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the time scales of the dynamic changes. Here we use the CO oxidation reaction over a Pd(100) surface exposed to pressures of 3 and 100 mbar of a CO + O2 gas mixture to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. For the CO oxidation reaction over Pd(100) our main finding is that that all surface phases – the CO-covered Pd surface, a surface oxide and a thick PdOx phase – catalyse the CO oxidation reaction, in dependence on the supply of gas phase reactants.

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