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Supporting Information
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84906362216
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15 indicated that the chemisorbed NO molecules cannot react with the atomic N due to a high activation barrier. They react with the N atoms above 350 K as their diffusion becomes active at the high temperatures.
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15 indicated that the chemisorbed NO molecules cannot react with the atomic N due to a high activation barrier. They react with the N atoms above 350 K as their diffusion becomes active at the high temperatures.
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19
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84906390832
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We conducted DFT calculations to check this reaction model qualitatively because NO dimer is one of the molecules that are not treated explicitly within the state-of-the-art DFT methods.17 The detailed calculation methods were described in the previous works.18,19 The DFT calculations were performed with the program package DMol3 in Materials Studio (version 2.2) of Accelrys Inc. A (2 × 2) surface unit cell of a slab of four layers' thickness (including 16 Rh atoms) was used. The slab was repeated periodically with a 30 A of vacuum region between the slabs. The adsorbates and the two top layers of metal surfaces were allowed to relax in all the calculations without symmetry restriction. Transition state search was performed with synchronous transition methods to estimate activation.17,18 We have found that the reaction scheme is energetically reasonable also for the DFT calculations, although the absolute adsorption energies are overestimated with
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17,18 We have found that the reaction scheme is energetically reasonable also for the DFT calculations, although the absolute adsorption energies are overestimated within the tendency of the state-of-the-art DFT method. The negative activation energy is also confirmed.
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20
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36449006894
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The N-K NEXAFS of the physisorbed NO monomer is expected to be similar to that of isolated NO in the gas phase. It exhibits a sharp N1s → π* peak at around 399 eV (Kosugi, N.; Adachi J.; Shigemasa E.; Yagisita. A. J. Chem. Phys. 1992, 97, 8842). Such a peak is not observed in the present spectra.
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The N-K NEXAFS of the physisorbed NO monomer is expected to be similar to that of isolated NO in the gas phase. It exhibits a sharp N1s → π* peak at around 399 eV (Kosugi, N.; Adachi J.; Shigemasa E.; Yagisita. A. J. Chem. Phys. 1992, 97, 8842). Such a peak is not observed in the present spectra.
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