We present a systematic performance analysis of first-principles basin-hopping (BH) runs, with the target to identify all low-energy isomers of small Si and Cu clusters described within density-functional theory. As representative and widely employed
move classes we focus on single-particle and collective moves, in which one or all atoms in the cluster at once are displaced in a random direction by some prescribed move distance, respectively. The analysis provides detailed insights into the bottlenecks and governing factors for the sampling efficiency, as well as simple rules-of-thumb for near-optimum move settings, that are intriguingly independent of the distinctly different chemistry of Si and Cu. At corresponding settings, the observed performance of the BH algorithm employing two simple, general-purpose move classes is already very good, and for the small systems studied essentially limited by frequent revisits to a few dominant isomers.
In previous work on adsorbate-induced surface core level shifts (SCLSs), the effects caused by O atom adsorption on Rh(111) and Ru(0001) were found to be additive: the measured shifts for first layer Ru atoms depended linearly on the number of direct
ly coordinated O atoms. Density-functional theory calculations quantitatively reproduced this effect, allowed separation of initial and final state contributions, and provided an explanation in terms of a roughly constant charge transfer per O atom. We have now conducted similar measurements and calculations for three well-defined adsorbate and coadsorbate layers containing O and H atoms: (1 x 1)-H, (2 x 2)-(O+H), and (2 x 2)-(O+3H) on Ru(0001). As H is stabilized in fcc sites in the prior two structures and in hcp sites in the latter, this enables us to not only study coverage and coadsorption effects on the adsorbate-induced SCLSs, but also the sensitivity to similar adsorption sites. Remarkably good agreement is obtained between experiment and calculations for the energies and geometries of the layers, as well as for all aspects of the SCLS values. The additivity of the next-neighbor adsorbate-induced SCLSs is found to prevail even for the coadsorbate structures. While this confirms the suggested use of SCLSs as fingerprints of the adsorbate configuration, their sensitivity is further demonstrated by the slightly different shifts unambiguously determined for H adsorption in either fcc or hcp hollow sites.
Far-infrared vibrational spectroscopy by multiple photon dissociation has proven to be a very useful technique for the structural fingerprinting of small metal clusters. Contrary to previous studies on cationic V, Nb and Ta clusters, measured vibrati
onal spectra of small cationic cobalt clusters show a strong dependence on the number of adsorbed Ar probe atoms, which increases with decreasing cluster size. Focusing on the series Co_4^+ to Co_8^+ we therefore use density-functional theory to analyze the nature of the Ar-Co_n^+ bond and its role for the vibrational spectra. In a first step, energetically low-lying isomer structures are identified through first-principles basin-hopping sampling runs and their vibrational spectra computed for a varying number of adsorbed Ar atoms. A comparison of these fingerprints with the experimental data enables in some cases a unique assignment of the cluster structure. Independent of the specific low-lying isomer, we obtain a pronounced increase of the Ar binding energy for the smallest cluster sizes, which correlates nicely with the observed increased influence of the Ar probe atoms on the IR spectra. Further analysis of the electronic structure motivates a simple electrostatic picture that not only explains this binding energy trend, but also why the influence of the rare-gas atom is much stronger than in the previously studied systems.
