Probing the Phase Transition to a Coherent 2D Kondo Lattice.

Kondo lattices are systems with unusual electronic properties that stem from strong electron correlation, typically studied in intermetallic 3D compounds containing lanthanides or actinides. Lowering the dimensionality of the system enhances the role of electron correlations providing a new tuning knob for the search of novel properties in strongly correlated quantum matter. The realization of a 2D Kondo lattice by stacking a single-layer Mott insulator on a metallic surface is reported. The temperature of the system is steadily lowered and by using high-resolution scanning tunneling spectroscopy, the phase transition leading to the Kondo lattice is followed. Above 27 K the interaction between the Mott insulator and the metal is negligible and both keep their original electronic properties intact. Below 27 K the Kondo screening of the localized electrons in the Mott insulator begins and below 11 K the formation of a coherent quantum electronic state extended to the entire sample, i.e., the Kondo lattice, takes place. By means of density functional theory, the electronic properties of the system and its evolution with temperature are explained. The findings contribute to the exploration of unconventional states in 2D correlated materials.

Imaging and controlling coherent phonon wave packets in single graphene nanoribbons.

The motion of atoms is at the heart of any chemical or structural transformation in molecules and materials. Upon activation of this motion by an external source, several (usually many) vibrational modes can be coherently coupled, thus facilitating the chemical or structural phase transformation. These coherent dynamics occur on the ultrafast timescale, as revealed, e.g., by nonlocal ultrafast vibrational spectroscopic measurements in bulk molecular ensembles and solids. Tracking and controlling vibrational coherences locally at the atomic and molecular scales is, however, much more challenging and in fact has remained elusive so far. Here, we demonstrate that the vibrational coherences induced by broadband laser pulses on a single graphene nanoribbon (GNR) can be probed by femtosecond coherent anti-Stokes Raman spectroscopy (CARS) when performed in a scanning tunnelling microscope (STM). In addition to determining dephasing (~440 fs) and population decay times (~1.8 ps) of the generated phonon wave packets, we are able to track and control the corresponding quantum coherences, which we show to evolve on time scales as short as ~70 fs. We demonstrate that a two-dimensional frequency correlation spectrum unequivocally reveals the quantum couplings between different phonon modes in the GNR.

Nearly-freestanding supramolecular assembly with tunable structural properties.

The synthesis and design of two-dimensional supramolecular assemblies with specific functionalities is one of the principal goals of the emerging field of molecule-based electronics, which is relevant for many technological applications. Although a large number of molecular assemblies have been already investigated, engineering uniform and highly ordered two-dimensional molecular assemblies is still a challenge. Here we report on a novel approach to prepare wide highly crystalline molecular assemblies with tunable structural properties. We make use of the high-reactivity of the carboxylic acid functional moiety and of the predictable structural features of non-polar alkane chains to synthesize 2D supramolecular assemblies of 4-(decyloxy)benzoic acid (4DBA;C[Formula: see text]H[Formula: see text]O[Formula: see text]) on a Au(111) surface. By means of scanning tunneling microscopy, density functional theory calculations and photoemission spectroscopy, we demonstrate that these molecules form a self-limited highly ordered and defect-free two-dimensional single-layer film of micrometer-size, which exhibits a nearly-freestanding character. We prove that by changing the length of the alkoxy chain it is possible to modify in a controlled way the molecular density of the "floating" overlayer without affecting the molecular assembly. This system is especially suitable for engineering molecular assemblies because it represents one of the few 2D molecular arrays with specific functionality where the structural properties can be tuned in a controlled way, while preserving the molecular pattern.

Massive and massless plasmons in germanene nanosheets.

Atomically thin crystals may exhibit peculiar dispersive electronic states equivalent to free charged particles of ultralight to ultraheavy masses. A rare coexistence of linear and parabolic dispersions yields correlated charge density modes exploitable for nanometric light confinement. Here, we use a time-dependent density-functional approach, under several levels of increasing accuracy, from the random-phase approximation to the Bethe-Salpeter equation formalism, to assess the role of different synthesized germanene samples as platforms for these plasmon excitations. In particular, we establish that both freestanding and some supported germenene monolayers can sustain infrared massless modes, resolved into an out-of-phase (optical) and an in-phase (acoustic) component. We further indicate precise experimental geometries that naturally host infrared massive modes, involving two different families of parabolic charge carriers. We thus show that the interplay of the massless and massive plasmons can be finetuned by applied extrinsic conditions or geometry deformations, which constitutes the core mechanism of germanene-based optoelectronic and plasmonic applications.

Dielectric screening versus geometry deformation in two-dimensional allotropes of silicon and germanium.

The search for connections between electronic and structural features is a key factor in the synthesis of artificial materials for on-demand applications, with graphene and analogous elemental semimetals playing a distinguished role as building blocks of photonic and plasmonic systems. In particular, a diversity of arrangements and electronic-state dispersions is offered by currently synthesized two-dimensional allotropes of silicon and germanium, respectively known as silicene and germanene. These monolayers make the ideal playground to understand how their collective and single-particle electronic states, excited by electron or light beams, may be controlled by geometry rather than doping or gating. Here, we provide such a study using time-dependent density-functional theory, in the random-phase approximation, to identify the structural dependent properties of charge-density plasmon oscillations and optical absorption in flat to buckled silicene and germanene lattices. We further single out flat germanene as an unprecedented two-dimensional conductor, hosting Dirac cone fermions in parallel with metal-like charge carriers, which contribute to strong intraband plasmon modes and one-electron excitations in the far-infrared limit. Finally, we show how this atypical scenario can be tuned by external stress or strain.

Calibration of Fermi Velocity to Explore the Plasmonic Character of Graphene Nanoribbon Arrays by a Semi-Analytical Model.

We present an analysis of the electronic and plasmonic behavior of periodic planar distributions of sufficiently wide graphene nanoribbons, for which a thorough ab initio investigation is practically unfeasible. Our approach is based on a semi-analytical model whose only free parameter is the charge carrier velocity, which we estimate by density-functional theory calculations on graphene. By this approach, we show that the plasmon resonance energies of the scrutinized systems fall in the lower THz band, relevant for optoelectronic and photonic applications. We further observe that these energies critically depend on the charge carrier concentration, ribbon width, electron relaxation rate, and in-plane transferred momentum angle, thus, suggesting a tunability of the associated light-matter modes.

Removal of mercury(II) from aqueous solution by partially reduced graphene oxide.

Mercury (Hg(II)) has been classified as a pollutant and its removal from aqueous sources is considered a priority for public health as well as ecosystem protection policies. Oxidized graphenes have attracted vast interest in water purification and wastewater treatment. In this report, a partially reduced graphene oxide is proposed as a pristine adsorbent material for Hg(II) removal. The proposed material exhibits a high saturation Hg(II) uptake capacity of 110.21 mg g-1, and can effectively reduce the Hg(II) concentration from 150 mg L-1 to concentrations smaller than 40 mg L-1, with an efficiency of about 75% within 20 min. The adsorption of Hg(II) on reduced graphene oxide shows a mixed physisorption-chemisorption process. Density functional theory calculations confirm that Hg atom adsorbs preferentially on clean zones rather than locations containing oxygen functional groups. The present work, therefore, presents new findings for Hg(II) adsorbent materials based on partially reduced graphene oxide, providing a new perspective for removing Hg(II).

Efficient photogeneration of nonacene on nanostructured graphene.

The on-surface photogeneration of nonacene from α-bisdiketone precursors deposited on nanostructured epitaxial graphene grown on Ru(0001) has been studied by means of low temperature scanning tunneling microscopy and spectroscopy. The presence of an unoccupied surface state, spatially localized in the regions where the precursors are adsorbed, and energetically accessible in the region of the electromagnetic spectrum where n-π* transitions take place, allows for a 100% conversion of the precursors into nonacenes. With the help of state-of-the-art theoretical calculations, we show that such a high yield is due to the effective population of the surface state by the incoming light and the ensuing electron transfer to the unoccupied states of the precursors through an inelastic scattering mechanism. Our findings are the experimental confirmation that surface states can play a prominent role in the surface photochemistry of complex molecular systems, in accordance with early theoretical predictions made on small molecules.

Electronic Properties of Sulfur Covered Ru(0001) Surfaces.

The structural properties of sulfur superstructures adsorbed on Ru(0001) have been widely studied in the past. However, much less effort has been devoted to determine their electronic properties. To understand the connection between structural and electronic properties, we have carried out density functional theory periodic boundary calculations mimicking the four long-range ordered sulfur superstructures identified experimentally by means of scanning tunneling microscopy (STM) techniques. Our simulations allow us to characterize the nature of the sulfur-Ru bond, the charge transfer between the Ru substrate and the sulfur adlayers, the interface states, and a parabolic state recently identified in STM experiments. A simple analysis, based on a one-dimensional model, reveals that this parabolic state is related to a potential well state, formed in the surface when the concentration of sulfur atoms is large enough to generate a new minimum in the surface potential.

Tunable plasmons in regular planar arrays of graphene nanoribbons with armchair and zigzag-shaped edges.

Recent experimental evidence for and the theoretical confirmation of tunable edge plasmons and surface plasmons in graphene nanoribbons have opened up new opportunities to scrutinize the main geometric and conformation factors, which can be used to modulate these collective modes in the infrared-to-terahertz frequency band. Here, we show how the extrinsic plasmon structure of regular planar arrays of graphene nanoribbons, with perfectly symmetric edges, is influenced by the width, chirality and unit-cell length of each ribbon, as well as the in-plane vacuum distance between two contiguous ribbons. Our predictions, based on time-dependent density functional theory, in the random phase approximation, are expected to be of immediate help for measurements of plasmonic features in nanoscale architectures of nanoribbon devices.

Statistics of work and orthogonality catastrophe in discrete level systems: an application to fullerene molecules and ultra-cold trapped Fermi gases.

The sudden introduction of a local impurity in a Fermi sea leads to an anomalous disturbance of its quantum state that represents a local quench, leaving the system out of equilibrium and giving rise to the Anderson orthogonality catastrophe. The statistics of the work done describe the energy fluctuations produced by the quench, providing an accurate and detailed insight into the fundamental physics of the process. We present here a numerical approach to the non-equilibrium work distribution, supported by applications to phenomena occurring at very diverse energy ranges. One of them is the valence electron shake-up induced by photo-ionization of a core state in a fullerene molecule. The other is the response of an ultra-cold gas of trapped fermions to an embedded two-level atom excited by a fast pulse. Working at low thermal energies, we detect the primary role played by many-particle states of the perturbed system with one or two excited fermions. We validate our approach through the comparison with some photoemission data on fullerene films and previous analytical calculations on harmonically trapped Fermi gases.