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A unique property of metal nanoclusters is the "superatom" shell structure of their delocalized electrons. The electronic shell levels are highly degenerate and therefore represent sharp peaks in the density of states. This can enable exceptionally strong electron pairing in certain clusters composed of tens to hundreds of atoms. In a finite system, such as a free nanocluster or a nucleus, pairing is observed most clearly via its effect on the energy spectrum of the constituent fermions. Accordingly, we performed a photoionization spectroscopy study of size-resolved aluminum nanoclusters and observed a rapid rise in the near-threshold density of states of several clusters (Al37,44,66,68) with decreasing temperature. The characteristics of this behavior are consistent with compression of the density of states by a pairing transition into a high-temperature superconducting state with Tc≳100K. This value exceeds that of bulk aluminum by two orders of magnitude. These results highlight the potential of novel pairing effects in size-quantized systems and the possibility to attain even higher critical temperatures by optimizing the particles' size and composition. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks. [ABSTRACT FROM AUTHOR]

Quantitative density measurements from electron scattering show that shear bands in deformed Al88Y7Fe5 metallic glass exhibit alternating high and low density regions, ranging from -9% to +6% relative to the undeformed matrix. Small deflections of the shear band from the main propagation direction coincide with switches in density from higher to lower than the matrix and vice versa, indicating that faster and slower motion (stick slip) occurs during the propagation. Nanobeam diffraction analyses provide clear evidence that the density changes are accompanied by structural changes, suggesting that shear alters the packing of tightly bound short- or medium-range atomic clusters. This bears a striking resemblance to the packing behavior in granular shear bands formed upon deformation of granular media. [ABSTRACT FROM AUTHOR]

The phenomenon of acoustic activation of surface diffusion is investigated in a combined computational and experimental study. The ability of pulsed laser-generated surface acoustic waves (SAWs) to enhance the mobility of small atomic clusters is demonstrated by directly tracking, with fluorescence microscopy, individual Au8 clusters moving on a (111) silicon substrate. A 19-fold increase in the effective diffusion coefficient is measured in room temperature experiments in the presence of SAWs generated by nanosecond pulse laser irradiation at a 100 Hz repetition rate. A strong enhancement of cluster mobility by SAWs is also observed in large-scale molecular dynamics simulations of surface diffusion of small atomic clusters. The analysis of the computational results demonstrates that the nonlinear sharpening of SAWs and the corresponding enrichment of the SAW spectra by high frequency harmonics which are capable of dynamic coupling to the cluster vibrations are responsible for the efficient acoustic activation of surface mobility in the simulations. The increase in the effective diffusion coefficient is proportional to the number of the SAW pulses passing through the diffusion region per unit time and a dramatic 4500-fold diffusion enhancement (corresponds to an equivalent temperature increase by ~103 K) is predicted in the simulations for 15 GHz SAWs. The ability of SAWs to affect atomic-level surface processes has far-reaching implications for the design of new techniques where the acoustic energy serves as an effective substitution for thermal activation in applications where heating must be avoided or rapid switching of surface conditions is required. [ABSTRACT FROM AUTHOR]

he Al5Co2 crystal is a complex intermetallic compound, whose structure can be described by a stacking of chemically bonded atomic motifs. It is a potentially new catalytic material for heterogeneous hydrogenation. A single crystal of this phase has been grown by the Czochralski technique in order to study the influence of the three-dimensional bulk substructure on the two-dimensional surface using both experimental ultrahigh vacuum surface techniques and ab initio methods based on the density functional theory. Some bulk properties are first presented, focusing on chemical bond strengths, the determination of the Al and Co chemical potentials in Al5Co2, the vibrational properties, and the specific heat. Then, the combination of experimental and computational approaches allows the identification of the surface structure, which was found to depend on the surface preparation conditions. In all cases, the surface terminates at specific bulk layers (Al-rich puckered layers) where various fractions of specific sets of Al atoms are missing, identified as Al3 atoms left at the surface resulting from cluster truncation. Finally, electron density of states calculations and spectroscopic measurements were compared and indicate a strong sp-d hybridization of the topmost pure Al layer with subsurface Co atoms. This could influence the surface reactivity and the catalytic performances of this material. [ABSTRACT FROM AUTHOR]

In order to find the right support to form assemblies of superatoms with useful magnetic properties, adsorption of the magnetic superatom FeCa8 on different types of substrates is studied using first-principles electronic structure methods. FeCa8 interacts strongly with oxide and metal substrates and its structure and magnetic properties are destroyed. Interaction between FeCa8, and graphene and hexagonal BN (h-BN) are weak, and its structure is retained on these substrates. Dimers of FeCag are also found to be stable on both h-BN and graphene. While the magnetic interaction between two FeCa8 units deposited on h-BN involves only direct exchange, substrate mediated RKKY interaction also plays a role on graphene. Consequences of these for the magnetic properties of the assemblies are discussed. [ABSTRACT FROM AUTHOR]

In an ensemble of laser-driven atoms involving strongly interacting Rydberg states, the steady-state excitation probability is usually substantially suppressed. In contrast, here we identify a regime in which the Rydberg excited fraction is enhanced by the interaction. This effect is associated with the buildup of manybody coherences induced by coherent multiphoton excitations between collective states. The excitation enhancement should be observable under currently existing experimental conditions and may serve as a direct probe for the presence of coherent multiphoton dynamics involving collective quantum states. [ABSTRACT FROM AUTHOR]

The potential energy surface of a heteroparticle system will contain points that are local minima in both coordinate space and permutation space for the different species. We introduce the term biminima to describe these special points, and we formulate a deterministic scheme for finding them. Our search algorithm generates a converging sequence of particle-identity swaps, each accompanied by a number of local geometry relaxations. For selected binary atomic clusters of size N = NA + NB ⩽ 98, convergence to a biminimum on average takes 3NANB relaxations, and the number of biminima grows with the preference for mixing. The new framework unifies continuous and combinatorial optimization, providing a powerful tool for structure prediction and rational design of multicomponent materials. [ABSTRACT FROM AUTHOR]

We present a method to approximate the Hessian matrix of the Bom-Oppenheimer energy landscape by using a simple force field model whose parameters are fitted to on-the-fiight ab-initio results. The inversed Hessian matrix is used as the precondifioner of conjugate gradient algorithms to speed up the atomic structure relaxation, resulting in a speedup factor of 2 to 5 on systems of bulk, slab, sheets, and atomic clusters. Because the force field model employed is simple and general, the parameter fitting is straightforward; the method is applicable to a variety of complicated systems for minimum structure relaxation. In the metal cluster new structure search, the new method yields better structures than the one obtained before with conventional algorithms. [ABSTRACT FROM AUTHOR]

A logarithmic oscillator has the outstanding property that the expectation value of its kinetic energy is constant for all stationary states. Recently the ansatz that this property can be used to define a Hamiltonian thermostat has been put forward and a suggestion has been made that this logarithmic oscillator weakly coupled to a small system would serve as a thermostat as long as few degrees of freedom are involved as is the case in atomic clusters. We have applied these ideas to a cluster of four Lennard-Jones atoms and inspected two different models of coupling between the cluster and the logarithmic oscillator in three dimensions. In both cases we show that there is a clear generation of kinetic motion of the cluster center of mass, but that kinetic energy due to interatomic vibrations is not significantly affected by coupling to the logarithmic oscillator. This is a failure of the published ansatz, as the logarithmic oscillator is unable to modify the kinetic energy due to vibrations in small atomic clusters. [ABSTRACT FROM AUTHOR]

Using scanning tunneling microscopy supplemented with first-principles calculations, we examine all the thermally activated atomistic processes of Agn (n = 1–26) constructed atom-by-atom on a Si(111)-(7×7) substrate, and we exploit such cluster dynamical information to further determine the energetic stability (or magicity) of the clusters. By generalizing the traditional concept of cluster magicity solely based on cluster association/dissociation to also include various complex collective cluster motions, we identify the existence of two classes of magic clusters. The most stable class, Ag10 and Ag25, is defined by geometrical shell closure; the less stable class of Agn (n = 3, 5, 13, 16, 19) is associated with lower kinetic barriers against internal restructuring of, or atom detachment from, their respective clusters of neighboring sizes. Our detailed analysis also reveals that the substrate effect, rather than the number of bonds within the clusters, dominates the cluster stabilities. The conceptual advances gained in the present study are broadly applicable to many related cluster systems in contact with external media, and they are expected to be instrumental in tuning the dynamical behaviors of clusters in surface catalysis, nanoplasmonics, and other technological areas. [ABSTRACT FROM AUTHOR]

We report an intense broadband midinfrared absorption band in the Au10+ cluster in a region in which only molecular vibrations would normally be expected. Observed in the infrared multiple photon dissociation spectra of Au10Ar+, Au10(N2O)+, and Au10(OCS)+, the smooth feature stretches 700-3400 cm-1 (λ=14-2.9 μm). Calculations confirm unusually low-energy allowed electronic excitations consistent with the observed spectra. In Au10(OCS)+, IR absorption throughout the band drives OCS decomposition resulting in CO loss, providing an alternative method of bond activation or breaking. [ABSTRACT FROM AUTHOR]

Femtosecond laser pulses have opened new frontiers for the study of ultrafast phase transitions and nonequilibrium states of matter. In this Letter, we report on structural dynamics in atomic clusters pumped with intense near-infrared (NIR) pulses into a nanoplasma state. Employing wide-angle scattering with intense femtosecond x-ray pulses from a free-electron laser source, we find that highly excited xenon nanoparticles retain their crystalline bulk structure and density in the inner core long after the driving NIR pulse. The observed emergence of structural disorder in the nanoplasma is consistent with a propagation from the surface to the inner core of the clusters. [ABSTRACT FROM AUTHOR]

We report on the experimental observation of nontrivial three-photon correlations imprinted onto initially uncorrelated photons through an interaction with a single Rydberg superatom. Exploiting the Rydberg blockade mechanism, we turn a cold atomic cloud into a single effective emitter with collectively enhanced coupling to a focused photonic mode which gives rise to clear signatures in the connected part of the three-body correlation function of the outgoing photons. We show that our results are in good agreement with a quantitative model for a single, strongly coupled Rydberg superatom. Furthermore, we present an idealized but exactly solvable model of a single two-level system coupled to a photonic mode, which allows for an interpretation of our experimental observations in terms of bound states and scattering states. [ABSTRACT FROM AUTHOR]

The Materials Project crystal structure database has been searched for materials possessing layered motifs in their crystal structures using a topology-scaling algorithm. The algorithm identifies and measures the sizes of bonded atomic clusters in a structure's unit cell, and determines their scaling with cell size. The search yielded 826 stable layered materials that are considered as candidates for the formation of two-dimensional monolayers via exfoliation. Density-functional theory was used to calculate the exfoliation energy of each material and 680 monolayers emerge with exfoliation energies below those of already-existent two-dimensional materials. The crystal structures of these two-dimensional materials provide templates for future theoretical searches of stable two-dimensional materials. The optimized structures and other calculated data for all 826 monolayers are provided at our database. [ABSTRACT FROM AUTHOR]

We report on the six-dimensional (6D) structural refinement of three members of the i-R-Cd quasicrystals (R = Gd, Dy, Tm) via synchrotron x-ray diffraction from single-grain samples, and show that this series is isostructural to the i-YbCd5.7 quasicrystal. However, our refinements suggest that the R occupancy on the Yb icosahedron sites within the Tsai-type atomic cluster is approximately 80%, with the balance taken up by Cd. Similarities between the i-R-Cd series and i-ScZn7.33, and their differences with i-YbCd5.7 and i-Ca15Cd85, indicate that there are at least two subclasses of Tsai-type icosahedral quasicrystals. We further show from x-ray resonant magnetic scattering (XRMS) measurements on a set of closely related Tb1-xYxCd6 1/1 approximants that the dilution of the magnetic R ions on the icosahedron within the Tsai-type cluster by nonmagnetic Y disrupts the commensurate magnetic ordering in the approximant phase. [ABSTRACT FROM AUTHOR]

Due to a large discrepancy between theory and experiment, the electronic character of crystalline boron carbide B13C2 has been a controversial topic in the field of icosahedral boron-rich solids. We demonstrate that this discrepancy is removed when configurational disorder is accurately considered in the theoretical calculations. We find that while the ordered ground state B13C2 is metallic, the configurationally disordered B13C2, modeled with a superatom-special quasirandom structure method, goes through a metal to nonmetal transition as the degree of disorder is increased with increasing temperature. Specifically, one of the chain-end carbon atoms in the CBC chains substitutes a neighboring equatorial boron atom in a B12 icosahedron bonded to it, giving rise to a B11Ce(BBC) unit. The atomic configuration of the substitutionally disordered B13C2 thus tends to be dominated by a mixture between B12(CBC) and B11Ce(BBC). Due to splitting of valence states in B11Ce(BBC), the electron deficiency in B12(CBC) is gradually compensated. [ABSTRACT FROM AUTHOR]