Adsorption of NO on the Rh-13, Pd-13, Ir-13, and Pt-13 Clusters: A Density Functional Theory Investigation

The adsorption of NO on transition-metal (TM) surfaces has been widely studied by experimental and theoretical techniques; however, our atomistic understanding of the interaction of nitrogen monoxide (NO) with small TM clusters is far from satisfactory, which compromises a deep understanding of real catalyst devices. In this study, we report a density functional theory study of the adsorption properties of NO on the TM13 (TM = Rh, Pd, Ir, Pt) clusters employing the projected augmented wave method. We found that the interaction of NO with TM13 is much more complex than that for NO/TM(111). In particular, for low symmetry TM13 clusters, there is a strong rearrangement of the electronic charge density upon NO adsorption and, as a consequence, the adsorption energy shows a very complex dependence even for adsorption sites with the same local effective coordination. We found a strong enhancement of the binding energy of NO to the TM13 clusters compared with the TM(111) surfaces, as the antibonding NO states are not occupied for NO/TM13, and the general relationship based on the d-band model between adsorption energy and the center of gravity of the occupied d-states does not hold for the studied TM13 clusters, in particular, for clusters with low symmetry. In contrast with the adsorption energy trends, the geometric NO/TM13 parameters and the vibrational N-O frequencies for different coordination sites follow the same trend as for the respective TM(111) surfaces, while the changes in the frequencies between different surfaces and TM13 clusters reflect the strong NO-TM13 interaction.

Trans-Planckian problem in the healthy extension of Horava-Lifshitz gravity

Planck scale physics may influence the evolution of cosmological fluctuations in the early stages of cosmological evolution. Because of the quasiexponential redshifting, which occurs during an inflationary period, the physical wavelengths of comoving scales that correspond to the present large-scale structure of the Universe were smaller than the Planck length in the early stages of the inflationary period. This trans-Planckian effect was studied before using toy models. The Horava-Lifshitz (HL) theory offers the chance to study this problem in a candidate UV complete theory of gravity. In this paper we study the evolution of cosmological perturbations according to HL gravity assuming that matter gives rise to an inflationary background. As is usually done in inflationary cosmology, we assume that the fluctuations originate in their minimum energy state. In the trans-Planckian region the fluctuations obey a nonlinear dispersion relation of Corley-Jacobson type. In the "healthy extension" of HL gravity there is an extra degree of freedom which plays an important role in the UV region but decouples in the IR, and which influences the cosmological perturbations. We find that in spite of these important changes compared to the usual description, the overall scale invariance of the power spectrum of cosmological perturbations is recovered. However, we obtain oscillations in the spectrum as a function of wave number with a relative amplitude of order unity and with an effective frequency which scales nonlinearly with wave number. Taking the usual inflationary parameters we find that the frequency of the oscillations is so large as to render the effect difficult to observe.

Platinum-Based Nanoalloys PtnTM55-n (TM=Co, Rh, Au): A Density Functional Theory Investigation

Structural and electronic properties of the PtnTM55-n (TM = Co, Rh, Au) nanoalloys are investigated using density functional theory within the generalized gradient approximation and employing the all-electron projected augmented wave method. For TM = Co and Rh, the excess energy, which measures the relative energy stability of the nanoalloys, is negative for all Pt compositions. We found that the excess energy has similar values for a wide range of Pt compositions, i.e., n = 20-42 and n = 28-42 for Co and Rh, respectively, with the core shell icosahedron-like configuration (n = 42) being slightly more stable for both Co and Rh systems because of the larger release of the strain energy due to the smaller atomic size of the Co and Rh atoms. For TM = Au, the excess energy is positive for all compositions, except for n = 13, which is energetically favorable due to the formation of the core-shell structure (Pt in the core and Au atoms at the surface). Thus, our calculations confirm that the formation of core-shell structures plays an important role to increase the stability of nanoalloys. The center of gravity of the occupied d-states changes almost linearly as a function of the Pt composition, and hence, based on the d-band model, the magnitude of the adsorption energy of an adsorbate can be tuned by changing the Pt composition. The magnetic moments of PtnCo55-n decrease almost linearly as a function of the Pt composition; however, the same does not hold for PtRh and PtAu. We found an enhancement of the magnetic moments of PtRh by a few times by increasing Pt composition, which we explain by the compression effects induced by the large size of the Pt atoms compared with the Rh atoms.

Hard Thermal Loops in the n-Dimensional phi(3) Theory

We derive a closed-form result for the leading thermal contributions which appear in the n-dimensional I center dot (3) theory at high temperature. These contributions become local only in the long wavelength and in the static limits, being given by different expressions in these two limits.