Footprints of atomic-scale features in plasmonic nanoparticles as revealed by electron energy loss spectroscopy.

We present a first-principles theoretical study of the atomistic footprints in the valence electron energy loss spectroscopy (EELS) of nanometer-size metallic particles. Charge density maps of excited plasmons and EEL spectra for specific electron paths through a nanoparticle (Na380 atom cluster) are modeled using ab initio calculations within time-dependent density functional theory. Our findings unveil the atomic-scale sensitivity of EELS within this low-energy spectral range. Whereas localized surface plasmons (LSPs) are particularly sensitive to the atomistic structure of the surface probed by the electron beam, confined bulk plasmons (CBPs) reveal quantum size effects within the nanoparticle's volume. Moreover, we prove that classical local dielectric theories mimicking the atomistic structure of the nanoparticles reproduce the LSP trends observed in quantum calculations, but fall short in describing the CBP behavior observed under different electron trajectories.

Kondo Effect of Co-Porphyrin: Remarkable Sensitivity to Adsorption Sites and Orientations.

We investigated the Kondo effect of cobalt(II)-5-15-bis(4'-bromophenyl)-10,20-bis(4'-iodophenyl)porphyrin (CoTPPBr2I2) molecules on Au(111) with low-temperature scanning tunneling microscopy under ultrahigh vacuum conditions. The molecules exhibit four adsorption configurations at the top and bridge sites of the surface with different molecular orientations. The Kondo resonance shows extraordinary sensitivity to the adsorption configuration. By switching the molecule between different configurations, the Kondo temperature is varied over a wide range from ≈8 up to ≈250 K. Density functional theory calculations reveal that changes of the adsorption configuration lead to distinct variations of the hybridization between the molecule and the surface. Furthermore, we show that surface reconstruction plays a significant role for the molecular Kondo effect.

Molecular Doping in the Organic Semiconductor Diindenoperylene: Insights from Many-Body Perturbation Theory.

Molecular doping provides a route toward designing new organic compounds with improved performance for optoelectronics. Here, we investigate the p-type doping of crystalline diindenoperylene (DIP) with two recently proposed electron-accepting molecular dopants using many-body perturbation theory. For the pristine DIP crystal, the quasiparticle band structure and the optical absorption spectra are found in agreement with the experimental data. Using the same methodology, we then characterize the optical and electronic properties of the two doped DIP crystals. The bandgap of both doped crystals is narrowed considerably due to the formation of hybridized states at the valence band edge. Moreover, a hybrid unoccupied mid-gap band is created with a host-dopant charge-transfer characteristic, giving rise to broader absorption spectra and a much lower absorption onset as compared to pristine DIP. Our results highlight that the interaction and hybridization with the host environment, including many-body effects, must be carefully considered in order to identify appropriate molecular dopants for a given organic crystal.

From Solution to Surface: Persistence of the Diradical Character of a Diindenoanthracene Derivative on a Metallic Substrate.

Organic diradicals are envisioned as elementary building blocks for designing a new generation of spintronic devices and have been used in constructing prototypical field effect transistors and nonlinear optical devices. Open-shell systems, however, are also reactive, thus requiring design strategies to "protect" their radical character from the environment, especially when they are embedded in solid-state devices. Here, we report the persistence on a metallic surface of the diradical character of a diindeno[b,i]anthracene (DIAn) core protected by bulky end-groups. Our scanning tunneling spectroscopy measurements on single-molecules detected singlet-triplet excitations that were absent for DIAn species packed in assembled structures. Density functional theory simulations unravel that the molecular geometry on the metal substrate can crucially modify the value of the singlet-triplet gap via the delocalization of the radical sites. The persistence of the diradical character over metallic substrates is a promising finding for integrating radical-based materials into functional devices.

Mach-Zehnder-like interferometry with graphene nanoribbon networks.

We study theoretically electron interference in a Mach-Zehnder-like geometry formed by four zigzag graphene nanoribbons arranged in parallel pairs, one on top of the other, such that they form intersection angles of 60∘. Depending on the interribbon separation, each intersection can be tuned to act either as an electron beam splitter or as a mirror, enabling tuneable circuitry with interfering pathways. Based on the mean-field Hubbard model and Green's function techniques, we evaluate the electron transport properties of such eight-terminal devices and identify pairs of terminals that are subject to self-interference. We further show that the scattering matrix formalism in the approximation of independent scattering at the four individual junctions provides accurate results as compared with the Green's function description, allowing for a simple interpretation of the interference process between two dominant pathways. This enables us to characterize the device sensitivity to phase shifts from an external magnetic flux according to the Aharonov-Bohm effect as well as from small geometric variations in the two path lengths. The proposed devices could find applications as magnetic field sensors and as detectors of phase shifts induced by local scatterers on the different segments, such as adsorbates, impurities or defects. The setup could also be used to create and study quantum entanglement.

Controlling the Spin States of FeTBrPP on Au(111).

Spin-flip excitations of iron porphyrin molecules on Au(111) are investigated with a low-temperature scanning tunneling microscope. The molecules adopt two distinct adsorption configurations on the surface that exhibit different magnetic anisotropy energies. Density functional theory calculations show that the different structures and excitation energies reflect unlike occupations of the Fe 3d levels. We demonstrate that the magnetic anisotropy energy can be controlled by changing the adsorption site, the orientation, or the tip-molecule distance.

Addressing Electron Spins Embedded in Metallic Graphene Nanoribbons.

Spin-hosting graphene nanostructures are promising metal-free systems for elementary quantum spintronic devices. Conventionally, spins are protected from quenching by electronic band gaps, which also hinder electronic access to their quantum state. Here, we present a narrow graphene nanoribbon substitutionally doped with boron heteroatoms that combines a metallic character with the presence of localized spin 1/2 states in its interior. The ribbon was fabricated by on-surface synthesis on a Au(111) substrate. Transport measurements through ribbons suspended between the tip and the sample of a scanning tunneling microscope revealed their ballistic behavior, characteristic of metallic nanowires. Conductance spectra show fingerprints of localized spin states in the form of Kondo resonances and inelastic tunneling excitations. Density functional theory rationalizes the metallic character of the graphene nanoribbon due to the partial depopulation of the valence band induced by the boron atoms. The transferred charge builds localized magnetic moments around the boron atoms. The orthogonal symmetry of the spin-hosting state's and the valence band's wave functions protects them from mixing, maintaining the spin states localized. The combination of ballistic transport and spin localization into a single graphene nanoribbon offers the perspective of electronically addressing and controlling carbon spins in real device architectures.

Time-dependent density functional theory calculations of electronic friction in non-homogeneous media.

The excitation of low-energy electron-hole pairs is one of the most relevant processes in the gas-surface interaction. An efficient tool to account for these excitations in simulations of atomic and molecular dynamics at surfaces is the so-called local density friction approximation (LDFA). The LDFA is based on a strong approximation that simplifies the dynamics of the electronic system: a local friction coefficient is defined using the value of the electronic density for the unperturbed system at each point of the dynamics. In this work, we apply real-time time-dependent density functional theory to the problem of the electronic friction of a negative point charge colliding with spherical jellium metal clusters. Our non-adiabatic, parameter-free results provide a benchmark for the widely used LDFA approximation and allow the discussion of various processes relevant to the electronic response of the system in the presence of the projectile.

Spin-Polarizing Electron Beam Splitter from Crossed Graphene Nanoribbons.

Junctions composed of two crossed graphene nanoribbons (GNRs) have been theoretically proposed as electron beam splitters where incoming electron waves in one GNR can be split coherently into propagating waves in two outgoing terminals with nearly equal amplitude and zero back-scattering. Here we scrutinize this effect for devices composed of narrow zigzag GNRs taking explicitly into account the role of Coulomb repulsion that leads to spin-polarized edge states within mean-field theory. We show that the beam-splitting effect survives the opening of the well-known correlation gap and, more strikingly, that a spin-dependent scattering potential emerges which spin polarizes the transmitted electrons in the two outputs. By studying different ribbons and intersection angles we provide evidence that this is a general feature with edge-polarized nanoribbons. A near-perfect polarization can be achieved by joining several junctions in series. Our findings suggest that GNRs are interesting building blocks in spintronics and quantum technologies with applications for interferometry and entanglement.

On-surface synthesis of Mn-phthalocyanines with optically active ligands.

The synthesis of novel organic prototypes combining different functionalities is key to achieve operational elements for applications in organic electronics. Here we set the stage towards individually addressable magneto-optical transducers by the on-surface synthesis of optically active manganese-phthalocyanine derivatives (MnPc) obtained directly on a metallic substrate. We created these 2D nanostructures under ultra-high vacuum conditions with atomic precision starting from a simple phthalonitrile precursor with reversible photo-induced reactivity in solution. These precursors maintain their integrity after powder sublimation and coordinate with the Mn ions into tetrameric complexes and then transform into MnPcs on Ag(111) after a cyclotetramerization reaction. Using scanning tunnelling microscopy and spectroscopy together with DFT calculations, we identify the isomeric configuration of two bi-stable structures and show that it is possible to switch them reversibly by mechanical manipulation. Moreover, the robust magnetic moment brought by the central Mn ion provides a feasible pathway towards magneto-optical transducer fabrication. This work should trigger further research confirming such magneto-optical effects in MnPcs both on surfaces and in liquid environments.

Magnetic correlations in single-layer NbSe2.

By means of spin-resolved density functional theory calculations using both atomic orbitals and plane-wave basis codes, we study the electronic and magnetic ground state of single-layer NbSe2. We find that, for all the functionals considered, the most stable solution in this two-dimensional (2D) superconductor is the ferrimagnetic ground state with a magnetic moment of 1.09 µBat the Nb atoms and of 0.05 µBat the Se atoms pointing in the opposite direction. Our calculations show that the ferrimagnetic state precludes the development of charge density wave (CDW) order and their coexistence in the single-layer limit, unless graphene is considered as a substrate. The spin-resolved calculated density of states (DOS), a key fingerprint of the electronic and magnetic structure of a material, unambiguously reproduces the experimental DOS measured by scanning tunneling spectroscopy in single-layer NbSe2. Our work sets magnetism into play in this prototypical correlated 2D material, which is crucial to understand the formation mechanisms of 2D superconductivity and CDW order.

From starphenes to non-benzenoid linear conjugated polymers by substrate templating.

Combining on-surface synthetic methods with the power of scanning tunneling microscopy to characterize novel materials at the single molecule level, we show how to steer the reactivity of one anthracene-based precursor towards different product nanostructures. Whereas using a Au(111) surface with three-fold symmetry results in the dominant formation of a starphene derivative, the two-fold symmetry of a reconstructed Au(110) surface allows the selective growth of non-benzenoid linear conjugated polymers. We further assess the electronic properties of each of the observed product structures via tunneling spectroscopy and DFT calculations, altogether advancing the synthesis and characterization of molecular structures of notable scientific interest that have been only scarcely investigated to date, as applies both to starphenes and to non-benzenoid conjugated polymers.

On-Surface Synthesis of Chlorinated Narrow Graphene Nanoribbon Organometallic Hybrids.

Graphene nanoribbons (GNRs) and their derivatives attract growing attention due to their excellent electronic and magnetic properties as well as the fine-tuning of such properties that can be obtained by heteroatom substitution and/or edge morphology modification. Here, we introduce graphene nanoribbon derivatives-organometallic hybrids with gold atoms incorporated between the carbon skeleton and side Cl atoms. We show that narrow chlorinated 5-AGNROHs (armchair graphene nanoribbon organometallic hybrids) can be fabricated by on-surface polymerization with omission of the cyclodehydrogenation reaction by a proper choice of tailored molecular precursors. Finally, we describe a route to exchange chlorine atoms connected through gold atoms to the carbon skeleton by hydrogen atom treatment. This is achieved directly on the surface, resulting in perfect unsubstituted hydrogen-terminated GNRs. This will be beneficial in the molecule on-surface processing when the preparation of final unsubstituted hydrocarbon structure is desired.

Magnetism of Topological Boundary States Induced by Boron Substitution in Graphene Nanoribbons.

Graphene nanoribbons (GNRs), low-dimensional platforms for carbon-based electronics, show the promising perspective to also incorporate spin polarization in their conjugated electron system. However, magnetism in GNRs is generally associated with localized states around zigzag edges, difficult to fabricate and with high reactivity. Here we demonstrate that magnetism can also be induced away from physical GNR zigzag edges through atomically precise engineering topological defects in its interior. A pair of substitutional boron atoms inserted in the carbon backbone breaks the conjugation of their topological bands and builds two spin-polarized boundary states around them. The spin state was detected in electrical transport measurements through boron-substituted GNRs suspended between the tip and the sample of a scanning tunneling microscope. First-principle simulations find that boron pairs induce a spin 1, which is modified by tuning the spacing between pairs. Our results demonstrate a route to embed spin chains in GNRs, turning them into basic elements of spintronic devices.

Key Role of the Surface Band Structure in Spin-Dependent Interfacial Electron Transfer: Ar/Fe(110) and Ar/Co(0001).

The injection of spin-polarized electrons across interfaces is central to many technologies, and hence, it is important to understand the main ingredients controlling it. Here, we demonstrate that the spin dependence of ultrafast electron transfer at Ar/Co(0001) and Ar/Fe(110) interfaces is rooted in the details of the spin-split surface band structures. The injection dynamics are particularly sensitive to the sizes (in reciprocal space) of projected electronic band gaps around Γ̅. Our ab initio calculations back that minority electrons are injected significantly faster than majority electrons in line with recently reported experimental injection times. A simple tunnelling model incorporating the spin-dependent gap sizes confirms that this ingredient is crucial to rationalize the experimental results.

Catalytic Oxidation of CO on a Curved Pt(111) Surface: Simultaneous Ignition at All Facets through a Transient CO-O Complex*.

The catalytic oxidation of CO on transition metals, such as Pt, is commonly viewed as a sharp transition from the CO-inhibited surface to the active metal, covered with O. However, we find that minor amounts of O are present in the CO-poisoned layer that explain why, surprisingly, CO desorbs at stepped and flat Pt crystal planes at once, regardless of the reaction conditions. Using near-ambient pressure X-ray photoemission and a curved Pt(111) crystal we probe the chemical composition at surfaces with variable step density during the CO oxidation reaction. Analysis of C and O core levels across the curved crystal reveals that, right before light-off, subsurface O builds up within (111) terraces. This is key to trigger the simultaneous ignition of the catalytic reaction at different Pt surfaces: a CO-Pt-O complex is formed that equals the CO chemisorption energy at terraces and steps, leading to the abrupt desorption of poisoning CO from all crystal facets at the same temperature.

Siesta: Recent developments and applications.

A review of the present status, recent enhancements, and applicability of the Siesta program is presented. Since its debut in the mid-1990s, Siesta's flexibility, efficiency, and free distribution have given advanced materials simulation capabilities to many groups worldwide. The core methodological scheme of Siesta combines finite-support pseudo-atomic orbitals as basis sets, norm-conserving pseudopotentials, and a real-space grid for the representation of charge density and potentials and the computation of their associated matrix elements. Here, we describe the more recent implementations on top of that core scheme, which include full spin-orbit interaction, non-repeated and multiple-contact ballistic electron transport, density functional theory (DFT)+U and hybrid functionals, time-dependent DFT, novel reduced-scaling solvers, density-functional perturbation theory, efficient van der Waals non-local density functionals, and enhanced molecular-dynamics options. In addition, a substantial effort has been made in enhancing interoperability and interfacing with other codes and utilities, such as wannier90 and the second-principles modeling it can be used for, an AiiDA plugin for workflow automatization, interface to Lua for steering Siesta runs, and various post-processing utilities. Siesta has also been engaged in the Electronic Structure Library effort from its inception, which has allowed the sharing of various low-level libraries, as well as data standards and support for them, particularly the PSeudopotential Markup Language definition and library for transferable pseudopotentials, and the interface to the ELectronic Structure Infrastructure library of solvers. Code sharing is made easier by the new open-source licensing model of the program. This review also presents examples of application of the capabilities of the code, as well as a view of on-going and future developments.

Probing the Magnetism of Topological End States in 5-Armchair Graphene Nanoribbons.

We extensively characterize the electronic structure of ultranarrow graphene nanoribbons (GNRs) with armchair edges and zigzag termini that have five carbon atoms across their width (5-AGNRs), as synthesized on Au(111). Scanning tunneling spectroscopy measurements on the ribbons, recorded on both the metallic substrate and a decoupling NaCl layer, show well-defined dispersive bands and in-gap states. In combination with theoretical calculations, we show how these in-gap states are topological in nature and localized at the zigzag termini of the nanoribbons. In addition to rationalizing the driving force behind the topological class selection of 5-AGNRs, we also uncover the length-dependent behavior of these end states which transition from singly occupied spin-split states to a closed-shell form as the ribbons become shorter. Finally, we demonstrate the magnetic character of the end states via transport experiments in a model two-terminal device structure in which the ribbons are suspended between the scanning probe and the substrate that both act as leads.