Structure of amorphous GeSe9 by neutron diffraction and first-principles molecular dynamics: Impact of trajectory sampling and size effects.

The structure of glassy GeSe9 was investigated by combining neutron diffraction with density-functional-theory-based first-principles molecular dynamics. In the simulations, three different models of N = 260 atoms were prepared by sampling three independent temporal trajectories, and the glass structures were found to be substantially different from those obtained for models in which smaller numbers of atoms or more rapid quench rates were employed. In particular, the overall network structure is based on Sen chains that are cross-linked by Ge(Se4)1/2 tetrahedra, where the latter are predominantly corner as opposed to edge sharing. The occurrence of a substantial proportion of Ge-Se-Se connections does not support a model in which the material is phase separated into Se-rich and GeSe2-rich domains. The appearance of a first-sharp diffraction peak in the Bhatia-Thornton concentration-concentration partial structure factor does, however, indicate a non-uniform distribution of the Ge-centered structural motifs on an intermediate length scale.

Soluble surfactant spreading: How the amphiphilicity sets the Marangoni hydrodynamics.

Amphiphiles are molecules combining hydrophilic and hydrophobic parts. The way they arrange in bulk and at interfaces is related to the balance between these two parts, and can be quantified by introducing the critical micellar concentration (cmc). Amphiphiles (also named "surfactants") are also at the origin of dynamical effects: local gradients of interfacial concentrations create the so-called Marangoni flows. Here we study the coupling between the molecule amphiphilicity and these Marangoni flows. We investigate in detail a spreading configuration, where a local excess of surfactants is locally sustained, and follow how these surfactants spread at the interface and diffuse in bulk. We have measured the features of this flow (maximal distance and maximal speed), for different types of surfactant, and as a function of all experimentally available parameters, as well as for two different configurations. In parallel, we propose a detailed hydrodynamical model. For all the measured quantities, we have found a good agreement between the data and the model, evidencing that we have captured the key mechanisms under these spreading experiments. In particular, the cmc turns out to be-as for the static picture of a surfactant-a key element even under dynamical conditions, allowing us to connect the molecule amphiphilicity to its ability to create Marangoni flows.

Exohedral M-C60 and M2-C60 (M = Pt, Pd) systems as tunable-gap building blocks for nanoarchitecture and nanocatalysis.

Transition metal-fullerenes complexes with metal atoms bound on the external surface of C60 are promising building blocks for next-generation fuel cells and catalysts. Yet, at variance with endohedral M@C60, they have received a limited attention. By resorting to first principles simulations, we elucidate structural and electronic properties for the Pd-C60, Pt-C60, PtPd-C60, Pd2-C60, and Pt2-C60 complexes. The most stable structures feature the metal atom located above a high electron density site, namely, the π bond between two adjacent hexagons (π-66 bond). When two metal atoms are added, the most stable configuration is those in which metal atoms still stand on π-66 bonds but tends to clusterize. The electronic structure, rationalized in terms of localized Wannier functions, provides a clear picture of the underlying interactions responsible for the stability or instability of the complexes, showing a strict relationship between structure and electronic gap.

Origin of structural analogies and differences between the atomic structures of GeSe4 and GeS4 glasses: A first principles study.

First-principles molecular dynamics simulations based on density functional theory are employed for a comparative study of structural and bonding properties of two stoichiometrically identical chalcogenide glasses, GeSe4 and GeS4. Two periodic cells of 120 and 480 atoms are adopted. Both glasses feature a coexistence of Ge-centered tetrahedra and Se(S) homopolar connections. Results obtained for N = 480 indicate substantial differences at the level of the Se(S) environment, since Ge-Se-Se connections are more frequent than the corresponding Ge-S-S ones. The presence of a more prominent first sharp diffraction peak in the total neutron structure factor of glassy GeS4 is rationalized in terms of a higher number of large size rings, accounting for extended Ge-Se correlations. Both the electronic density of states and appropriate electronic localization tools provide evidence of a higher ionic character of Ge-S bonds when compared to Ge-Se bonds. An interesting byproduct of these investigations is the occurrence of discernible size effects that affect structural motifs involving next nearest neighbor distances, when 120 or 480 atoms are used.

Metal-organic molecule-metal nano-junctions: a close contact between first-principles simulations and experiments.

The realization of metal-molecule junctions for future electronic devices relies on our ability to assemble these heterogeneous objects at a molecular level and understand their structure and the behavior of the electronic states at the interface. Delocalized interface states near the metal Fermi level are a key ingredient for tailoring charge injection, and such a delocalization depends on a large number of chemical, structural and morphological parameters, all influencing the spatial extension of the electron wavefunctions. Our large-scale dynamical simulations, combined with experiments, show that a double-decker organometallic compound (ferrocene) can be deposited on a Cu(111) surface, providing an ideal system to investigate the adsorption, the interface states and localized spin states at a metal-organometallic interface. Adsorbed ferrocene is shown to have a peculiar pattern and realizes a 2D-like interface state strongly resembling Shockley's surface state of Cu. By a subsequent deposition of single metal atoms on the adsorbed ferrocene, we analyze the sensitivity of the interface state to local modifications of the interface potential. This provides an insight into adsorption, spin configuration and charge redistribution processes, showing how to tune the electron behavior at a metal-molecule interface.

The structure of liquid GeSe revisited: a first principles molecular dynamics study.

Early first-principles molecular dynamics results on liquid GeSe were characterized by shortcomings in the description of Ge-Ge (and to a lesser extent Se-Se) short range correlations. In that case the exchange-correlation functional adopted was the one devised by Perdew and Wang (PW91). In the search of improvements in the atomic-scale modelling of this liquid, we have produced new sets of data by employing two different schemes for the exchange-correlation part within the density functional theory approach. The two functionals selected are those proposed by Becke, Lee, Yang, and Parr (BLYP) and by Perdew, Burke, and Ernzerhof (PBE). The PBE results turned out to be quite similar to the PW91 ones. The BLYP results feature instead a better account of the Ge-Ge first shell of neighbors, correctly exhibiting two clear maxima separated by a deep minimum. Due to the increase in the number of the tetrahedral structural units, the atomic mobility of Ge and Se atoms in the network is reduced with respect to the PW91 case. This brings the diffusion coefficients of the two species down to values close to those of liquid Ge2Se3 and liquid GeSe2.

Investigation of size effects on the structure of liquid GeSe2 calculated via first-principles molecular dynamics.

The structural properties of liquid GeSe(2) have been calculated by first-principles molecular dynamics by using a periodic simulation box containing N = 480 atoms. This has allowed a comparison with previous results obtained on a smaller system size (N = 120) [M. Micoulaut, R. Vuilleumier, and C. Massobrio, Phys. Rev. B 79, 214205 (2009)]. In the domain of first-principles molecular dynamics, we obtain an assessment of system size effects of unprecedented quality. Overall, no drastic differences are found between the two sets of results, confirming that N = 120 is a suitable size to achieve a realistic description of this prototypical disordered network. However, for N = 480, short range properties are characterized by an increase of chemical order, the number of Ge tetrahedra coordinated to four Se atoms being larger. At the intermediate range order level, size effect mostly modify the low wavevector region (k ~1 Å(-1)) in the concentration-concentration partial structure factor.