Non-Adiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence

We present a perturbation approach rooted in time-dependent density-functional theory to calculate electron hole (eh)-pair excitation spectra during the non-adiabatic vibrational damping of adsorbates on metal surfaces. Our analysis for the benchmark systems CO on Cu(100) and Pt(111) elucidates the surprisingly strong influence of rather short electronic coherence times. We demonstrate how in the limit of short electronic coherence times, as implicitly assumed in prevalent quantum nuclear theories for the vibrational lifetimes as well as electronic friction, band structure effects are washed out. Our results suggest that more accurate lifetime or chemicurrent-like experimental measurements could characterize the electronic coherence.Comment: Article as accepted for publication in Physical Review Letter

Simulation of Cu-Mg metallic glass: Thermodynamics and Structure

We have obtained effective medium theory (EMT) interatomic potential parameters suitable for studying Cu-Mg metallic glasses. We present thermodynamic and structural results from simulations of such glasses over a range of compositions. We have produced low-temperature configurations by cooling from the melt at as slow a rate as practical, using constant temperature and pressure molecular dynamics. During the cooling process we have carried out thermodynamic analyses based on the temperature dependence of the enthalpy and its derivative, the specific heat, from which the glass transition temperature may be determined. We have also carried out structural analyses using the radial distribution function (RDF) and common neighbor analysis (CNA). Our analysis suggests that the splitting of the second peak, commonly associated with metallic glasses, in fact has little to do with the glass transition itself, but is simply a consequence of the narrowing of peaks associated with structural features present in the liquid state. In fact the splitting temperature for the Cu-Cu RDF is well above $T_g$. The CNA also highlights a strong similarity between the structure of the intermetallic alloys and the amorphous alloys of similar composition. We have also investigated the diffusivity in the supercooled regime. Its temperature dependence indicates fragile-liquid behavior, typical of binary metallic glasses. On the other hand, the relatively low specific heat jump of around $1.5 k_B/\mathrm{at.}$ indicates apparent strong-liquid behavior, but this can be explained by the width of the transition due to the high cooling rates.Comment: 12 pages (revtex, two-column), 12 figures, submitted to Phys. Rev.

First-principles statistical mechanics study of the stability of a sub-nanometer thin surface oxide in reactive environments: CO oxidation at Pd(100)

We employ a multiscale modeling approach to study the surface structure and composition of a Pd(100) model catalyst in reactive environments. Under gas phase conditions representative of technological CO oxidation (~1 atm, 300-600 K) we find the system on the verge of either stabilizing sub-nanometer thin oxide structures or CO adlayers at the surface. Under steady-state operation this suggests the presence or continuous formation and reduction of oxidic patches at the surface, which could be key to understand the observable catalytic function.Comment: 4 pages including 2 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm

The European venture capital and private equity country attractiveness index(es)

We calculate composite indexes to compare the attractiveness of 25 European countries for institutional investments into the Venture Capital and Private Equity asset class. To achieve this we use 42 different criteria and propose an aggregation structure that allows for benchmarking on more granular levels. The United Kingdom leads our ranking, followed by Ireland, Denmark, Sweden and Norway. While Germany is slightly above the average European attractiveness level, the scores for France, Italy, Spain, and Greece are rather disappointing. Our analyses reveal that while the United Kingdom is similar to the other European countries with respect to many criteria, there are two major differences which ultimately affect its attractiveness: its investor protection and corporate governance rules; and the size and liquidity of its capital market. The state of the capital market is likewise a proxy for the professionalism of the financial community, deal flow and exit opportunities. We determine a reasonable correlation between our attractiveness index scores and actual Venture Capital and Private Equity fundraising activities and prove the robustness of our calculations. Our findings across all the European countries suggest that while investor protection and capital markets are in fact very important determinants of attractiveness, there are numerous other criteria to consider.Venture Capital; Private Equity; Alternative Asset; International Asset Allocation;

Agassiz, Garman, Albatross, and the Collection of Deep-sea Fishes

The first of Alexander Agassiz’ voyages on the U.S. Fish Commission steamer Albatross in 1891 yielded significant scientific results. This paper reviews the background of the voyage, including the career path that led Agassiz to the back deck of the Albatross. We also give a brief account of the life and work of Samuel Garman. Garman wrote up the ichthyological material from this Albatross voyage in a magnificent book on deep-sea fishes published in 1899. This book was exceptional in its coverage, anatomical detail, and recognition of phylogenetically important morphology

Electronic friction-based vibrational lifetimes of molecular adsorbates: Beyond the independent atom approximation

We assess the accuracy of vibrational damping rates of diatomic adsorbates on metal surfaces as calculated within the local-density friction approximation (LDFA). An atoms-in-molecules (AIM) type charge partitioning scheme accounts for intra-molecular contributions and overcomes the systematic underestimation of the non-adiabatic losses obtained within the prevalent independent atom approximation. The quantitative agreement obtained with theoretical and experimental benchmark data suggests the LDFA-AIM as an efficient and reliable approach to account for electronic dissipation in ab initio molecular dynamics simulations of surface chemical reactions.Comment: 5 pages including 2 figure

Effect of surface nanostructure on temperature programmed reaction spectroscopy: First-principles kinetic Monte Carlo simulations of CO oxidation at RuO2(110)

Using the catalytic CO oxidation at RuO2(110) as a showcase, we employ first-principles kinetic Monte Carlo simulations to illustrate the intricate effects on temperature programmed reaction spectroscopy data brought about by the mere correlations between the locations of the active sites at a nanostructured surface. Even in the absence of lateral interactions, this nanostructure alone can cause inhomogeneities that cannot be grasped by prevalent mean-field data analysis procedures, which thus lead to wrong conclusions on the reactivity of the different surface species.Comment: 4 pages including 3 figures; related publications can be found at http://www.fhi-berlin.mpg.de/th/th.htm