Towards an exact treatment of exchange and correlation in materials: Application to the "CO adsorption puzzle" and other systems

It is shown that the errors of present-day exchange-correlation (xc) functionals are rather short ranged. For extended systems the correction can therefore be evaluated by analyzing properly chosen clusters and employing highest-quality quantum chemistry methods. The xc correction rapidly approaches a universal dependence with cluster size. The method is applicable to bulk systems as well as to defects in the bulk and at surfaces. It is demonstrated here for CO adsorption at transition-metal surfaces, where present-day xc functionals dramatically fail to predict the correct adsorption site, and for the crystal bulk cohesive energy.Comment: slightly revised version: 4 pages including 3 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

Carbon Monoxide Oxidation Promoted by Surface Polarization Charges in a CuO/Ag Hybrid Catalyst.

Composite structures have been widely utilized to improve material performance. Here we report a semiconductor-metal hybrid structure (CuO/Ag) for CO oxidation that possesses very promising activity. Our first-principles calculations demonstrate that the significant improvement in this system's catalytic performance mainly comes from the polarized charge injection that results from the Schottky barrier formed at the CuO/Ag interface due to the work function differential there. Moreover, we propose a synergistic mechanism underlying the recovery process of this catalyst, which could significantly promote the recovery of oxygen vacancy created via the M-vK mechanism. These findings provide a new strategy for designing high performance heterogeneous catalysts

Vibrational anharmonicity of small gold and silver clusters using the VSCF method

We study the vibrational spectra of small neutral gold (Au2–Au10) and silver (Ag2–Au5) clusters using the vibrational self-consistent field method (VSCF) in order to account for anharmonicity. We report harmonic, VSCF, and correlation-corrected VSCF calculations obtained using a vibrational configuration interaction approach (VSCF/VCI). Our implementation of the method is based on an efficient calculation of the potential energy surfaces (PES), using periodic density functional theory (DFT) with a plane-wave pseudopotential basis. In some cases, we use an efficient technique (fast-VSCF) assisted by the Voter–Chen potential in order to get an efficient reduction of the number of pair-couplings between modes. This allows us to efficiently reduce the computing time of 2D-PES without degrading the accuracy. We found that anharmonicity of the gold clusters is very small with maximum rms deviations of about 1 cm−1, although for some particular modes anharmonicity reaches values slightly larger than 2 cm−1. Silver clusters show slightly larger anharmonicity. In both cases, large differences between calculated and experimental vibrational frequencies (when available) stem more likely from the quality of the electronic structure method used than from vibrational anharmonicity. We show that noble gas embedding often affects the vibrational properties of these clusters more than anharmonicity, and discuss our results in the context of experimental studies

Exact Diagonalization Dynamical Mean Field Theory for Multi-Band Materials: Effect of Coulomb correlations on the Fermi surface of Na_0.3CoO_2

Dynamical mean field theory combined with finite-temperature exact diagonalization is shown to be a suitable method to study local Coulomb correlations in realistic multi-band materials. By making use of the sparseness of the impurity Hamiltonian, exact eigenstates can be evaluated for significantly larger clusters than in schemes based on full diagonalization. Since finite-size effects are greatly reduced this approach allows the study of three-band systems down to very low temperatures, for strong local Coulomb interactions and full Hund exchange. It is also shown that exact diagonalization yields smooth subband quasi-particle spectra and self-energies at real frequencies. As a first application the correlation induced charge transfer between t2g bands in Na_0.3CoO_2 is investigated. For both Hund and Ising exchange the small eg' Fermi surface hole pockets are found to be slightly enlarged compared to the non-interacting limit, in agreement with previous Quantum Monte Carlo dynamical mean field calculations for Ising exchange, but in conflict with photoemission data.Comment: 9 pages, 7 figure