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Scanning tunneling microscope data from a dinuclear Co(II) complex adsorbed on Au(111) are analysed using density functional theory calculations. We find that the interaction with the substrate substantially changes the geometry of the non-planar molecule. Its electronic states, however, remain fairly similar to those calculated for a gas-phase molecule. The calculations reproduce intriguing contrasts observed in experimental maps of the differential conductance dI/dV and reveal the relative importance of geometric and electronic factors that impinge on the image contrasts. For a meaningful comparison, it is important that the calculations closely mimic the experimental mode of measurement., Comment: 9 pages, 7 figures

Exploring the limits of the microscopic reversibility principle, we investigated the interplay between thermal and electron tunneling excitations for the unidirectional rotation of a molecule-rotor on the Au(111) surface. We identified a range of moderate voltages and temperatures where heating the surface enhances the unidirectional rotational rate of a chemisorbed DMNI-P rotor. At higher voltage, inelastic tunneling effects dominate while at higher temperature the process becomes stochastic. At each electron transfer event during tunneling, the quantum mixing of ground and excited electronic states brings part of the surface thermal energy in the excited electronic states of the molecule-rotor. Thermal energy contributes therefore to the semi-classical unidirectional rotation without contradicting the microscopic reversibility principle.

The realization of electron-spin resonance at the single-atom level using scanning tunneling microscopy has opened new avenues for coherent quantum sensing and quantum state manipulation at the ultimate size limit. This allows to build many-body Hamiltonians and the study of their complex physical behavior. Recently, a novel qubit platform has emerged from this field, raising questions about the driving mechanism from single-atom magnets. In this work, we demonstrate how single-atom magnets can be used to drive a nearby single spin qubit efficiently, while also addressing critical aspects related to the optimization of experimental parameters.

Surface-adsorbed rare-earth nanostructures are ideal platforms to investigate the interplay between intra-atomic interactions and multi-orbital spin configurations. However, addressing these properties has posed severe experimental and theoretical challenges. Here, we use the orbital selectivity offered by X-ray absorption spectroscopy to quantify the Coulomb integrals of Nd atoms on conductive surfaces, as well as the variation of individual orbital occupation upon cluster nucleation. Using X-ray magnetic circular dichroism we identify magnetic moments of the order of \MK{few tens of}~$\mu_{\rm{B}}$ at the $5d$ orbitals and their magnetic coupling with the $4f$ spins. Our results validate orbital-resolved X-ray spectroscopy as a reliable method for quantifying complex multi-orbital interactions in surface-adsorbed lanthanides.

The properties of 2D materials are strongly influenced by their substrate, leading to a variety of "proximity effects" like screening, charge transfer, and hybridization. Surprisingly, there is a dearth of theoretical studies on these effects. Particularly, previous theoretical research on the Star of David (SOD) structure in 1T-NbSe$_2$ has focused on single-layer configurations or stacking with the same 1T phase without any real substrate. Here, we depart from these approaches and explore how these proximity effects shape the electronic and magnetic properties of the 1T-NbSe$_2$ phase when it is grown on the metallic 1H-NbSe$_2$ substrate. Using Density Functional Calculations, we establish a common framework to define the key characteristics of both free-standning 1T-NbSe$_2$ and 1H-NbSe$_2$. We then identify the optimal stacking arrangement for these two layers, revealing a transfer from the 1T to the 1H phase and a reorganization of charge within each layer. Our findings indicate that the magnetic moment of the SOD structure is still robust; however, is diminished due to a reduction in the on-site Coulomb interaction of the Hubbard bands. Additionally, the interlayer coupling induces metallicity in the 1T phase and increases the decoupling of the lower Hubbard band from the valence band.

The role of self-consistency in Bogoliubov-de Gennes equations is frequently underestimated in the investigation of in-gap states created by magnetic impurities in s-wave superconductors. Our research focuses on the impact of self-consistency on the in-gap states produced by magnetic stuctures on superconductors, specifically evaluating the density of states, the in-gap bands, and their topological attributes. Here, we show results ranging from single impurity to finite chains, and infinite ferromagnetic spin chains in wide-band s-wave superconductors. These results show that the order parameter contains important information regarding quantum phase transitions and their topological nature, underscoring the importance of self-consistency in such studies.

We create two molecular devices with superconducting junctions, using nickelocene molecules, single Fe atoms, and Pb electrodes at low temperature. We find contrasting behavior based on the coordination of the Fe atom: one device shows low-bias features in its differential conductance due to the superposition of multiple Andreev reflections (MAR) and Fe-induced in-gap states. The other reveals interference between MAR and in-gap states, showcasing the diversity achievable in atomically engineered devices with identical components.

Computational models are an essential tool for the design, characterization, and discovery of novel materials. Hard computational tasks in materials science stretch the limits of existing high-performance supercomputing centers, consuming much of their simulation, analysis, and data resources. Quantum computing, on the other hand, is an emerging technology with the potential to accelerate many of the computational tasks needed for materials science. In order to do that, the quantum technology must interact with conventional high-performance computing in several ways: approximate results validation, identification of hard problems, and synergies in quantum-centric supercomputing. In this paper, we provide a perspective on how quantum-centric supercomputing can help address critical computational problems in materials science, the challenges to face in order to solve representative use cases, and new suggested directions., Comment: 65 pages, 15 figures; comments welcome

Motivated by recent developments in measurements of electron spin resonances of individual atoms and molecules with the scanning tunneling microscope (ESR-STM), we study electron transport through an impurity under periodic driving as a function of the transport parameters in a model junction. The model consists of a single-orbital quantum impurity connected to two electrodes via time-dependent hopping terms. The hopping terms are treated at the lowest order in perturbation theory to recover a Lindblad-like quantum master equation with electron transport. As in the experiment, the ESR-STM signal is given by the variation of the long-time DC current with the driving frequency. The density-matrix coherences play an important role in the evaluation of the ESR-STM signal. Electron correlation is included in our impurity mode. The charging energy $U$ has significant influence on the spin dynamics depending on the sign and magnitude of the applied DC bias. Our model allows direct insight into the origin of the ESR signal from the many-body dynamics of the impurity.

Understanding the fundamental mechanisms of optoelectronic excitation and relaxation pathways on the single-molecule level has only recently been started by combining scanning tunneling microscopy (STM) and spectroscopy (STS) with STM-induced luminescence (STML). In this paper, we investigate cationic and anionic fluorescence of individual zinc phthalocyanine (ZnPc) molecules adsorbed on ultrathin NaCl films on Ag(111) by using STML. They depend on the tip-sample bias polarity and appear at threshold voltages that are correlated with the onset energies of particular molecular orbitals, as identified by STS. We also find that the fluorescence is caused by a single electron tunneling process. Comparing with results from density functional theory calculations, we propose an alternative many-body picture to describe the charging and electroluminescence mechanism. Our study provides aspects toward well-defined voltage selectivity of bipolar electrofluorochromism, as well as fundamental insights regarding the role of transiently charged states of emitter molecules within OLED devices., Comment: Accepted version of the manuscript. Published open access

The development of electron spin resonance (ESR) combined with scanning tunneling spectroscopy (STM) is undoubtedly one of the main experimental breakthroughs in surface science of the last decade thanks to joining the extraordinarily high energy resolution of ESR (nano-eV scale) with the single-atom spatial resolution of STM (sub-\AA ngstr\"om scale). While the experimental results have \fer{significantly} grown with the number of groups that have succeeded in implementing the technique, the physical mechanism behind it is still unclear, with several different mechanisms proposed to explain it. Here, we start by revising the main characteristics of the experimental setups and observed features. Then, we review the main theoretical proposals, with both their strengths and weaknesses. One of our conclusions is that many of the proposed mechanisms share the same basic principles, \fer{the time-dependent electric field at the STM junction is modulating the coupling of the spin-polarized transport electrons with the local spin.} This explains why these mechanims are essentially equivalent in a broad picture. We analyze the subtle differences between some of them and how they compare with the different experimental observations., Comment: 32 pages, 4 figures, Review work

Electron paramagnetic resonance (EPR) can provide unique insight into the chemical structure and magnetic properties of dopants in oxide and semiconducting materials that are of interest for applications in electronics, catalysis, and quantum sensing. Here, we demonstrate that EPR in combination with scanning tunneling microscopy (STM) allows for probing the bonding and charge state of alkali metal atoms on an ultrathin magnesium oxide layer on a Ag substrate. We observe a magnetic moment of $1\mu_\mathrm{B}$ for Li$_2$, LiNa, and Na$_2$ dimers corresponding to spin radicals with a charge state of $+1e$. Single alkali atoms have the same charge state and no magnetic moment. The ionization of the adsorbates is attributed to charge transfer through the oxide to the metal substrate. Our work highlights the potential of EPR-STM to provide insight into dopant atoms that are relevant for the control of the electrical properties of surfaces and nanodevices., Comment: 18 pages, 5 figures

Our calculations of ferromagnetic spin chains on s-wave superconductors show that the energy oscillations of edge states with the chain's length are due to a moir\'e pattern emerging from Friedel-like oscillations and the discreteness of the spin-chain lattice. By modifying the spin lattice, the moir\'e dispersion of edge states can be controlled. In particular, we can engineer non-dispersive edge states that remain at fixed energy regardless of the size distribution of the spin chains. This is an important step in the study of edge states of spin chains that can be fabricated with a certain size dispersion.

Magnetic impurities create in-gap states on superconductors. Recent experiments explore the topological properties of one-dimensional arrays of magnetic impurities on superconductors, because in certain regimes p-wave pairing can be locally induced leading to new topological phases. A by-product of the new accessible phases is the appearance of zero-energy edge states that have non-Abelian exchange properties and can be used for topological quantum computation. Despite the large amount of theory devoted to these systems, most treatments use approximations that render their applicability limited when comparing with usual experiments of 1-D impurity arrays on wide-band superconductors. These approximations either involve tight-binding-like approximations where the impurity energy scales match the minute energy scale of the superconducting gap and are many times unrealistic, or they assume strongly-bound in-gap states. Here, we present a theory for s-wave superconductors based on a wide-band normal metal, with any possible energy scale for the magnetic impurities. The theory is based on free-electron Green's functions. We include Rashba coupling and compare with recent experimental results, permitting us to analyze the topological phases and the experimental edge states. The infinite-chain properties can be analytically obtained, giving us a way to compare with finite-chain calculations. We show that it is possible to converge to the infinite limit by doing finite numerical calculation, paving the way for numerical calculations not based on analytical Green's functions.

We present a theoretical framework to describe experiments directed to controlling single-atom spin dynamics by electrical means using a scanning tunneling microscope. We propose a simple model consisting of a quantum impurity connected to electrodes where an electrical time-dependent bias is applied. We solve the problem in the limit of weak coupling between the impurity and the electrodes by means of a quantum master equation that is derived by the non-equilibrium Green's function formalism. We show results in two cases. The first case is just a single atomic orbital subjected to a time-dependent electric field, and the second case consists of a single atomic orbital coupled to a second spin-1/2. The first case reproduces the main experimental features Ti atoms on MgO/Ag (100) while the second one directly addresses the experiments on two Ti atoms. These calculations permit us to explore the effect of different parameters on the driving of the atomic spins as well as to reproduce experimental fingerprints., Comment: This article is a resubmitted version that will be sent to publish soon

Electronic states in the gap of a superconductor inherit intriguing many-body properties from the superconductor. Here, we create these in-gap states by manipulating Cr atomic chains on the $\beta$-Bi$_2$Pd superconductor. We find that the topological properties of the in-gap states can greatly vary depending on the crafted spin chain. These systems make an ideal platform for non-trivial topological phases because of the large atom-superconductor interactions and the existence of a large Rashba coupling at the Bi-terminated surface. We study two spin chains, one with atoms two-lattice-parameter apart and one with square-root-of-two lattice parameters. Of these, only the second one is in a topologically non-trivial phase, in correspondence with the spin interactions for this geometry.

We create ordered islands of magnetically anisotropic nickelocene molecules on a Pb (111) substrate. By using inelastic electron tunneling spectra (IETS) and density functional theory, we characterize the magnetic response of these islands. This allows us to conclude that the islands present local and collective magnetic excitations. Furthermore, we show that nickelocene islands present complex non-collinear spin patterns on the superconducting Pb (111) surface, opening the possibility of using molecular arrays to engineer spin textures with important implications on topological superconductivity.

On a gold surface, supramolecules composed of 4-acetylbiphenyl molecules show structural directionality, reproducibility and robustness to external perturbations. We investigate the assembly of those molecules on the Au(111) surface and analyze how the observed supramolecular structures are the result of weak long-range dispersive forces stabilizing the 4-acetylbiphenyl molecules together. Metallic adatoms serve as stabilizing agents. Our analysis suggests new ways of creating complex molecular nano-objects that can eventually be used as devices or as seeds for extended hierarchical structures.

We report on the effect of sp3 hybridized carbon atoms in acene derivatives adsorbed on metal surfaces, namely decoupling the molecules from the supporting substrates. In particular, we have used a Ag(100) substrate and hydrogenated heptacene molecules, in which the longest conjugated segment determining its frontier molecular orbitals amounts to five consecutive rings. The non-planarity that the sp3 atoms impose on the carbon backbone results in electronically decoupled molecules, as demonstrated by the presence of charging resonances in dI/dV tunneling spectra and the associated double tunneling barriers, or in the Kondo peak that is due to a net spin S=1/2 of the molecule as its LUMO becomes singly charged. The spatially dependent appearance of the charging resonances as peaks or dips in the differential conductance spectra is further understood in terms of the tunneling barrier variation upon molecular charging, as well as of the different orbitals involved in the tunneling process.

The current $I$ through nickelocene molecules and its noise are measured with a low temperature scanning tunneling microscope on a Cu(100) substrate. Density functional theory calculations and many-body modeling are used to analyze the data. During contact formation, two types of current evolution are observed, an abrupt jump to contact and a smooth transition. These data along with conductance spectra ($dI/dV$) recorded deep in the contact range are interpreted in terms of a transition from a spin-1 to a spin-1/2 state that is Kondo screened. Many-body calculations show that the smooth transition is also consistent with a renormalization of spin excitations of a spin-1 molecule by Kondo exchange coupling. The shot noise is significantly reduced compared to the Schottky value of $2eI$ but no influence of the Kondo effect or spin excitations are resolved. The noise can be described in the Landauer picture in terms of spin-polarized transmission of $\approx$35% through two degenerate $d_\pi$-orbitals of the Nickelocene molecule., Comment: 10 pages, 10 figures; revised version published in Phys. Rev. B

In the present Colloquium, we focus on the properties of 1-D magnetic systems on solid surfaces. From the emulation of 1-D quantum phases to the potential realization of Majorana edge states, spin chains are unique systems to study. The advent of scanning tunnelling microscope (STM) based techniques has permitted us to engineer spin chains in an atom-by-atom fashion via atom manipulation and to access their spin states on the ultimate atomic scale. Here, we present the current state of research on spin correlations and dynamics of atomic spin chains as studied by the STM. After a brief review of the main properties of spin chains on solid surfaces, we classify spin chains according to the coupling of their magnetic moments with the holding substrate. This classification scheme takes into account that the nature and lifetimes of the spin-chain excitation intrinsically depend on the holding substrate. We first show the interest of using insulating layers on metals, which generally results in an increase in the spin state's lifetimes such that their quantized nature gets evident and they are individually accessible. Next, we show that the use of semiconductor substrates promises additional control through the tunable electron density via doping. When the coupling to the substrate is increased for spin chains on metals, the substrate conduction electron mediated interactions can lead to emergent exotic phases of the coupled spin chain-substrate conduction electron system. A particularly interesting example is furnished by superconductors. Magnetic impurities induce states in the superconducting gap. Due to the extended nature of the spin chain, the in-gap states develop into bands that can lead to the emergence of 1-D topological superconductivity and, consequently to the appearance of Majorana edge states.

A quantal model description of a discrete localized skyrmion singularity embedded in a ferromagnetic environment is proposed. It allows discussing the importance of various parameters in the appearance of a quantal skyrmion singularity. Analysis of the skyrmion reveals a few specific quantal properties: presence of a whole series of skyrmion states, non-classical nature of the local spins, presence of superposition states and presence of extra-skyrmion states due to the quantization of the central spin of the singularity. The interaction of an electron, tunneling or substrate, with the skyrmion is also described allowing a new view at the origin of the skyrmion stability as well as the possibility to discriminate between ferromagnetic and skyrmion phase in an Inelastic Electron Tunneling Spectroscopy (IETS) experiment, based on the skyrmion quantal properties.

Achieving the Ag(001)-supported synthesis of heptacene from two related reactants reveals the effect of the presence of Br atoms on the reaction process. The properties of reactant, intermediates and end-product are further characterized by scanning tunneling microscopy and spectroscopy.

We show that the magnetic ordering of coupled atomic dimers on a superconductor is revealed by their intra-gap spectral features. Chromium atoms on the superconductor $\beta$-Bi$_2$Pd surface display Yu-Shiba-Rusinov bound states, detected as pairs of intra-gap excitations in the tunneling spectra. We formed Cr dimers by atomic manipulation and found that their intra-gap features appear either shifted or split with respect to single atoms. The spectral variations reveal that the magnetic coupling of the dimer changes between ferromagnetic and antiferromagnetic depending on its disposition on the surface, in good agreement with density functional theory simulations. These results prove that superconducting intra-gap state spectroscopy is an accurate tool to detect the magnetic ordering of atomic scale structures.

A low-temperature scanning tunneling microscope was employed to study the differential conductance in an atomic junction formed by an adsorbed Co atom on a Cu(100) surface and a copper-covered tip. A zero-bias anomaly (ZBA) reveals spin scattering off the Co atom, which is assigned to a Kondo effect. The ZBA exhibits a characteristic asymmetric lineshape when electrons tunnel between tip and sample, while upon the tip-Co contact it symmetrizes and broadens. Through density functional theory calculations and the non-equilibrium non-crossing approximation we show that the lineshape broadening is mainly a consequence of the additional coupling to the tip, while non-equilibrium effects only modify the large-bias tails of the ZBA.

A magnetic atomic impurity inside a superconductor locally distorts superconductivity. They scatter Cooper pairs as a potential with broken time-reversal symmetry, what leads to localized bound states with subgap excitation energies, named hereon Shiba states. Most conventional approaches to study Shiba states treat magnetic impurities as point scatterers with an isotropic exchange interaction, while the complex internal structure of magnetic impurities is usually neglected. Here, we show that the number and the shape of Shiba states are correlated to the spin-polarized atomic orbitals of the impurity, hybridized with the superconducting host, as supported by Density Functional Theory simulations. Using high-resolution scanning tunneling spectroscopy, we spatially map the five Shiba excitations found on sub-surface chromium atoms in Pb(111), resolving both their particle and hole components. While the maps of particle components resemble the \textit{d} orbitals of embedded Cr atoms, the hole components differ strongly from them. The orbital fingerprints of Shiba states thus unveil the magnetic ground state of the impurity, and identify scattering channels and interactions, all valuable tools for designing atomic-scale superconducting devices., Comment: 5 pages manuscript and 7 pages supplementary information

We present novel methods implemented within the non-equilibrium Green function code (NEGF) transiesta based on density functional theory (DFT). Our flexible, next-generation DFT-NEGF code handles devices with one or multiple electrodes ($N_e\ge1$) with individual chemical potentials and electronic temperatures. We describe its novel methods for electrostatic gating, contour opti- mizations, and assertion of charge conservation, as well as the newly implemented algorithms for optimized and scalable matrix inversion, performance-critical pivoting, and hybrid parallellization. Additionally, a generic NEGF post-processing code (tbtrans/phtrans) for electron and phonon transport is presented with several novelties such as Hamiltonian interpolations, $N_e\ge1$ electrode capability, bond-currents, generalized interface for user-defined tight-binding transport, transmission projection using eigenstates of a projected Hamiltonian, and fast inversion algorithms for large-scale simulations easily exceeding $10^6$ atoms on workstation computers. The new features of both codes are demonstrated and bench-marked for relevant test systems., Comment: 24 pages, 19 figures

Heterogeneous atomic magnetic chains are built by atom manipulation on a Cu$_2$N/Cu (100) substrate. Their magnetic properties are studied and rationalized by a combined scanning tunneling microscopy (STM) and density functional theory (DFT) work completed by model Hamiltonian studies. The chains are built using Fe and Mn atoms ontop of the Cu atoms along the N rows of the Cu$_2$N surface. Here, we present results for FeMn$_x$ ($x$=1...6) chains emphasizing the evolution of the geometrical, electronic, and magnetic properties with chain size. By fitting our results to a Heisenberg Hamiltonian we have studied the exchange-coupling matrix elements $J$ for different chains. For the shorter chains, $x \leq 2$, we have included spin-orbit effects in the DFT calculations, extracting the magnetic anisotropy energy. Our results are also fitted to a simple anisotropic spin Hamiltonian and we have extracted values for the longitudinal-anisotropy $D$ and transversal-anisotropy $E$ constants. These parameters together with the values for $J$ allow us to compute the magnetic excitation energies of the system and to compare them with the experimental data., Comment: 10 pages 8 figures

Scanning tunnelling microscopy and density functional theory studies of manganese chains adsorbed on Cu$_2$N/Cu (100) reveal an unsuspected electronic edge state at $\sim 1$ eV above the Fermi energy. This Tamm-like state is strongly localised to the last Mn atom of the chain and fully spin polarised. However, no equivalence is found for occupied states, and the electronic structure at $\sim -1$ eV is mainly spin unpolarised due to the extended $p$-states of the N atoms that mediate the coupling between the Mn atoms in the chain. Odd-numbered Mn chains present an exponentially decreasing direct coupling with distance between the two edges, leading to a vanishing bonding/anti-bonding splitting of states while even-numbered Mn chains present perfect decoupling of both edges due to the the antiferromagnetic ordering of Mn chains.

Quantum entanglement permeates the complex ground states of correlated electron materials defying single-particle descriptions. Coupled magnetic atoms have potential as model systems for entanglement in condensed matter giving the opportunity to create artificial many-body states which can be controlled by tuning the underlying interactions. They provide an avenue to unravel the complexities of correlated-electron materials. Here we use low temperature scanning tunnelling microscopy (STM) and atomic manipulation to tune entanglement in chains of magnetic atoms. We find that a Kondo singlet state can emerge from this entanglement. The many electron Kondo state is based on the screening of the entangled spin ground state of the chain by substrate electrons and can be engineered to envelop at least ten magnetic atoms. The concomitant Kondo resonance measured in the differential conductance enables the electric read-out of entanglement. By tuning composition and coupling strength within atomic chains it is possible to create model spin chains with defined entanglement. This lays the foundation for a new class of experiments to construct exotic correlated-electron materials atom by atom., Comment: 15 pages, 4 figures, Supplementary Information

New advances in single-atom manipulation are leading to the creation of atomic structures on H passivated Si surfaces with functionalities important for the development of atomic and molecular based technologies. We perform total-energy and electron-transport calculations to reveal the properties and understand the features of atomic wires crafted by H removal from the surface. The presence of dopants radically change the wire properties. Our calculations show that dopants have a tendency to approach the dangling-bond wires, and in these conditions, transport is enhanced and spin selective. These results have important implications in the development of atomic-scale spintronics showing that boron, and to a lesser extent phosphorous, convert the wires in high-quality spin filters., Comment: 11 pages, 4 figures

We analyze the spontaneous switching between the two N\'eel states of Fe chains on Cu$_2$N/Cu(100), experimentally studied by Loth et al. [Science 335, 196 (2012)]. We show that, in the experimental low-temperature regime (T ~ 1K), decoherence induced by substrate electrons deeply modifies the dynamics of the chain magnetization. The Rabi oscillations associated to quantum tunneling of the isolated chain are replaced by an irreversible decay of considerably longer characteristic time. The computed switching rate is small, rapidly decreasing with chain length, with a 1/T behavior and in good agreement with the experiment. Quantum tunneling is only recovered as the switching mechanism at extremely low temperatures, the corresponding cross-over moving rapidly to further low temperatures as the chain length is increased., Comment: 5 pages 3 figures

Non-equilibrium Green's functions calculations based on density functional theory show a direct link between the initial stages of H$_2$ dissociation on a gold atomic wire and the electronic current supported by the gold wire. The simulations reveal that for biases below the stability threshold of the wire, the minimum-energy path for H$_2$ dissociation is not affected. However, the electronic current presents a dramatic drop when the molecule initiates its dissociation. This current drop is traced back to quantum interference between electron paths when the molecule starts interacting with the gold wire.

We have combined scanning tunneling microscopy with inelastic electron tunneling spectroscopy (IETS) and density functional theory (DFT) to study a tetracyanoethylene monolayer on Ag(100). Images show that the molecules arrange in locally ordered patterns with three non-equivalent, but undeterminable, adsorption sites. While scanning tunneling spectroscopy only shows subtle variations of the local electronic structure at the three different positions, we find that vibrational modes are very sensitive to the local atomic environment. IETS detects sizeable mode frequency shifts of the molecules located at the three topographically detected sites, which permits us to determine the molecular adsorption sites through identification with DFT calculations., Comment: Accepted for publication in Nano Letters. 16 pages, 5 figures

The controlled switching between two quasi-stable Neel states in adsorbed anti-ferromagnetic Fe chains has recently been achieved by Loth et al [Science 335, 196 (2012)]. In order to rationalize their data, we evaluate the rate of tunneling electron-induced switching between the N\'eel states. Good agreement is found with the experiment permitting us to identify three switching mechanisms: (i) low-bias direct electron-induced transitions, (ii) intermediate-bias switching via spin-wave-like excitation, and (iii) high-bias transitions mediated by domain wall formation. Spin correlations in the anti-ferromagnetic chains are the switching driving force leading to a marked chain-size dependence., Comment: 5 pages 3 figures

We evaluate the electron transmission through a dangling-bond wire on Si(100)-H (2x1). Finite wires are modelled by decoupling semi-infinite Si electrodes from the dangling-bond wire with passivating H atoms. The calculations are performed using density functional theory in a non-periodic geometry along the conduction direction. We also use Wannier functions to analyze our results and to build an effective tight-binding Hamiltonian that gives us enhanced insight in the electron scattering processes. We evaluate the transmission to the different solutions that are possible for the dangling-bond wires: Jahn-Teller distorted ones, as well as antiferromagnetic and ferromagnetic ones. The discretization of the electronic structure of the wires due to their finite size leads to interesting transmission properties that are fingerprints of the wire nature.

The advent of milli-kelvin scanning tunneling microscopes (STM) with inbuilt magnetic fields has opened access to the study of magnetic phenomena with atomic resolution at surfaces. In the case of single atoms adsorbed on a surface, the existence of different magnetic energy levels localized on the adsorbate is due to the breaking of the rotational invariance of the adsorbate spin by the interaction with its environment, leading to energy terms in the meV range. These structures were revealed by STM experiments in IBM Almaden in the early 2000's for atomic adsorbates on CuN surfaces. The experiments consisted in the study of the changes in conductance caused by inelastic tunnelling of electrons (IETS, Inelastic Electron Tunnelling Spectroscopy). Manganese and Iron adatoms were shown to have different magnetic anisotropies induced by the substrate. More experiments by other groups followed up, showing that magnetic excitations could be detected in a variety of systems: e.g. complex organic molecules showed that their magnetic anistropy was dependent on the molecular environment, piles of magnetic molecules showed that they interact via intermolecular exchange interaction, spin waves were excited on ferromagnetic surfaces and in Mn chains, and magnetic impurities have been analyzed on semiconductors. These experiments brought up some intriguing questions: the efficiency of magnetic excitations was very high, the excitations could or could not involve spin flip of the exciting electron and singular-like behavior was sometimes found at the excitation thresholds. These facts called for extended theoretical analysis; perturbation theories, sudden-approximation approaches and a strong coupling scheme successfully explained most of the magnetic inelastic processes. In addition, many-body approaches were also used to decipher the interplay between inelas, Comment: Review article to appear in Progress of Surface Science

We evaluate the electronic, geometric and energetic properties of quasi 1-D wires formed by dangling bonds on Si(100)-H (2 x 1). The calculations are performed with density functional theory (DFT). Infinite wires are found to be insulating and Peierls distorted, however finite wires develop localized electronic states that can be of great use for molecular-based devices. The ground state solution of finite wires does not correspond to a geometrical distortion but rather to an antiferromagnetic ordering. For the stability of wires, the presence of abundant H atoms in nearby Si atoms can be a problem. We have evaluated the energy barriers for intradimer and intrarow diffusion finding all of them about 1 eV or larger, even in the case where a H impurity is already sitting on the wire. These results are encouraging for using dangling-bond wires in future devices., Comment: 8 pages, 6 figures

Magnetic inelastic electron tunneling spectroscopy (IETS) shows sharp increases in conductance when a new conductance channel associated to a change in magnetic structure is open. Typically, the magnetic moment carried by an adsorbate can be changed by collision with a tunneling electron; in this process the spin of the electron can flip or not. A previous one-electron theory [Phys. Rev. Lett. {\bf 103}, 176601 (2009)] successfully explained both the conductance thresholds and the magnitude of the conductance variation. The elastic spin flip of conduction electrons by a magnetic impurity leads to the well known Kondo effect. In the present work, we compare the theoretical predictions for inelastic magnetic tunneling obtained with a one-electron approach and with a many-body theory including Kondo-like phenomena. We apply our theories to a singlet-triplet transition model system that contains most of the characteristics revealed in magnetic IETS. We use two self-consistent treatments (non-crossing approximation and self-consistent ladder approximation). We show that, although the one-electron limit is properly recovered, new intrinsic many-body features appear. In particular, sharp peaks appear close to the inelastic thresholds; these are not localized exactly at thresholds and could influence the determination of magnetic structures from IETS experiments.Analysis of the evolution with temperature reveals that these many-body features involve an energy scale different from that of the usual Kondo peaks. Indeed, the many-body features perdure at temperatures much larger than the one given by the Kondo energy scale of the system., Comment: 10 pages and 6 figures