A high throughput route to screen thermoelectric materials is developed and validated across a broad material set.

Engineering heterogeneous metal catalysts for high selectivity in thermal driven reactions typically involves the synthesis of nanostructures with well-controlled geometries and compositions. However, inherent relationships between the energetics of elementary steps limit the control of catalytic selectivity through these approaches. Photon excitation of metal catalysts can induce chemical reactivity channels that cannot be accessed using thermal energy, although the potential for targeted activation of adsorbate-metal bonds is limited because the processes of photon absorption and adsorbate-metal bond photoexcitation are typically separated spatially. Here, we show that the use of sub-5-nanometer metal particles as photocatalysts enables direct photoexcitation of hybridized adsorbate-metal states as the dominant mechanism driving photochemistry. Activation of targeted adsorbate-metal bonds through direct photoexcitation of hybridized electronic states enabled selectivity control in preferential CO oxidation in H2 rich streams. This mechanism opens new avenues to drive selective catalytic reactions that cannot be achieved using thermal energy.

The enthalpy of formation for 23 metal oxides, which include groups I and II as well as two transition metals (Ti and Ru), are calculated using random phase approximation (RPA). Compared to the PBE xc functional, the RPA reduces the mean absolute error (MAE) per oxygen from 0.44 to 0.15 eV. The calculated deviations from experiments are separated into two parts: a systematic and uniform error related to the reference energy of O and the errors specific to diffferent oxidation states O2-, O-2(2-), and O-2(-). Our results show that the RPA improves both the reference energy and the three oxidation states. DOI: 10.1103/PhysRevB.87.075207

The formation and oxidation reaction energies of 16 transition metal oxides (TMOs) are benchmarked against experiments with an increasing complexity of the exchange-correlation (xc) functionals: PBE, PBE + U with a single U for each transition metal element, PBE0 (25% exact exchange included), EXX (100% exact exchange), and EXX + RPA (random phase approximation for the correlation energy). Although rather challenging on standard CPU computing facilities, the RPA calculations were performed efficiently on graphic processing units (GPUs). For the formation energies, the PBE + U, PBE0, EXX + RPA improves significantly over PBE with mean absolute errors (MAE) of 0.83 (PBE), 0.39 (PBE + U), 0.34 (PBE0), and 0.39 (EXX + RPA) eV per oxygen. In addition, EXX+ RPA improves over the other xc functionals on the oxidation reaction energies, with MAE of 0.27 (PBE), 0.28 (PBE + U), 0.30 (PBE0), to 0.13 (EXX + RPA) eV per oxygen. The distinct trend observed for the calculated oxidation reaction energies compared to the formation energies is due to that the errors in formation energies for PBE and EXX+ RPA are systematic; while for PBE + U and PBE0 the deviations have both signs, so that the error cancellations between different valence states work better for PBE and EXX + RPA. Finally, we compared the performance of the EXX + RPA for total energies and G(0)W(0), which uses the random phase approximation in constructing the W kernel, for band gaps, and discuss a few challenges for the EXX + RPA method on TMOs.

The Random Phase Approximation (RPA) for correlation energy in the grid-based projector augmented wave (gpaw) code is accelerated by porting to the Graphics Processing Unit (GPU) architecture. The acceleration is achieved by grouping independent vectors/matrices and transforming the implementation from being memory bound to being computation/latency bound. With this approach, both the CPU and GPU implementations have been enhanced. We tested the GPU implementation on a few representative systems: molecules (O2), bulk solids (Li2O and MoO3) and molecules adsorbed on metal surfaces (N2/Ru(0001) and CO/Ni(111)). Improvements from 10× to 40× have been achieved (8-GPUs versus 8-CPUs). A realistic RPA calculation for CO/Ni(111) surface can be finished in 5.5 h using 8 GPUs. It is thus promising to employ the non-self-consistent RPA for routine surface chemistry simulations.

should read as "We present an efficient implementation of the Bethe-Salpeter equation (BSE) for optical properties of materials in the projector augmented wave method."The paper has been corrected as of 26 July 2012.

First-principles calculations of the conventional and acoustic surface plasmons (CSPs and ASPs) on the (111) surfaces of Cu, Ag, and Au are presented. The effect of $s-d$ interband transitions on both types of plasmons is investigated by comparing results from the local density approximation and an orbital dependent exchange-correlation (xc) potential that improves the position and width of the $d$ bands. The plasmon dispersions calculated with the latter xc-potential agree well with electron energy loss spectroscopy (EELS) experiments. For both the CSP and ASP, the same trend of Cu$<$Au$<$Ag is found for the plasmon energies and is attributed to the reduced screening by interband transitions from Cu, to Au and Ag. This trend for the ASP, however, contradicts a previous model prediction. While the ASP is seen as a weak feature in the EELS, it can be clearly identified in the static and dynamic dielectric band structure.

We present an efficient implementation of the Bethe-Salpeter equation (BSE) for optical properties of materials in the projector augmented wave method GPAW. Single-particle energies and wave functions are obtained from the GLLBSC functional which explicitly includes the derivative discontinuity, is computationally inexpensive, and yields excellent fundamental gaps. Electron-hole interactions are included through the BSE using the statically screened interaction evaluated in the random phase approximation. For a representative set of semiconductors and insulators we find excellent agreement with experiments for the dielectric functions, onset of absorption, and lowest excitonic features. For the two-dimensional systems of graphene and hexagonal boron-nitride (h-BN) we find good agreement with previous many-body calculations. For the graphene/h-BN interface, we find that the fundamental and optical gaps of the h-BN layer are reduced by 2.0 eV and 0.7 eV, respectively, compared to freestanding h-BN. This reduction is due to image charge screening which shows up in the GLLBSC calculation as a reduction (vanishing) of the derivative discontinuity.

Linear-response time-dependent density functional theory is used to investigate the relation between molecular bonding and surface plasmons for the model system H/Ag(111). We employ an orbital-dependent exchangecorrelation functional to obtain a correct description of the Ag 3d band, which is crucial to avoid overscreening the plasmon by the s-d interband transitions. For the clean surface, this approach reproduces the experimental plasmon energies and dispersion to within 0.15 eV. Adsorption of hydrogen shifts and damps the Ag(111) surface plasmon and induces a new peak in the loss function at 0.6 eV below the Ag(111) plasmon peak. This feature originates from interband transitions between states located on the hydrogen atoms and states on the Ag surface atoms.

We present an implementation of the linear density response function within the projector-augmented wave (PAW) method with applications to the linear optical and dielectric properties of both solids, surfaces, and interfaces. The response function is represented in plane waves while the single-particle eigenstates can be expanded on a real space grid or in atomic orbital basis for increased efficiency. The exchange-correlation kernel is treated at the level of the adiabatic local density approximation (ALDA) and crystal local field effects are included. The calculated static and dynamical dielectric functions of Si, C, SiC, AlP and GaAs compare well with previous calculations. While optical properties of semiconductors, in particular excitonic effects, are generally not well described by ALDA, we obtain excellent agreement with experiments for the surface loss function of the Mg(0001) surface with plasmon energies deviating by less than 0.2 eV. Finally, we apply the method to study the influence of substrates on the plasmon excitations in graphene. On SiC(0001), the long wavelength $\pi$ plasmons are significantly damped although their energies remain almost unaltered. On Al(111) the $\pi$ plasmon is completely quenched due to the coupling to the metal surface plasmon.

We investigate the role of substrates on the collective excitations of graphene by using a first-principles implementation of the density response function within the random-phase approximation. Specifically, we consider graphene adsorbed on SiC(0001) and Al(111) as representative examples of a semiconducting and metallic substrate. On SiC(0001), the long wavelength π plasmons are significantly damped although their energies remain almost unaltered. On Al(111), the long wavelength π plasmons are completely quenched due to the coupling to the metal surface plasmon. The strong damping of the plasmon excitations occurs despite the fact that the single-particle band structure of graphene is completely unaffected by the substrates illustrating the nonlocal nature of the effect.