Using periodic, self-consistent density functional theory calculations, the adsorption of several atomic (H, S, N, O and C) and molecular (CO2, N2, NH3, HCN, CO and NO) species and molecular fragments (NH2, NH, CN, CNH2, HNO, NOH, CH3, CH2, CH and OH) on the (0001) facet of rhenium at a coverage of 0.25 ML has been studied. Preferred binding sites with their corresponding binding energy and deformation energy of the surface, as well as an estimated diffusion barrier of each species have been determined. Atomic species and molecular fragments tend to bind to threefold sites, whereas molecular species tend to bind to top sites. The binding strength, with respect to the corresponding gas phase species and in increasing order for all species studied, is: CO2 < N2 < NH3 < CO < CH3 < HCN < NO < H < NH2 < OH < CH2 < CNH2 < CN < HNO < NH < NOH < S < N < O < CH < C. The vibrational frequencies of all species in their most energetically favorable adsorbed configuration have been calculated. Finally, the thermochemistry of adsorption and decomposition of NO, NO + H, NH3, N2, CO2, CO and CH4 on Re(0001) has been analyzed.
Density functional theory Rhenium Catalysis Adsorption Binding energies Vibrational frequencies
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Both authors want to congratulate Prof. Jens K. Nørskov on the occasion of his 60th birthday. They have tremendously benefited from his inspiring work in heterogeneous catalysis so far and wish him the very best for the future. Work at UW-Madison was supported by DOE-BES, Office of Chemical Sciences. KRH acknowledges partial support from DAAD. We thank Prof. Lars C. Grabow and Jeff Herron for helpful discussions and careful reading of the manuscript and Lang Xu for carrying out some of the calculations of this work. Computational work was performed in part using supercomputing resources from the following institutions: EMSL, a National scientific user facility at Pacific Northwest National Laboratory (PNNL); the Center for Nanoscale Materials at Argonne National Laboratory (ANL); and the National Energy Research Scientific Computing Center (NERSC). EMSL is sponsored by the Department of Energy’s Office of Biological and Environmental Research located at PNNL. CNM, and NERSC are supported by the U.S. Department of Energy, Office of Science, under contracts DE-AC02-06CH11357 and DE-AC02-05CH11231, respectively.
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