Widening of the fundamental gap in cluster GW for metal-molecular interfaces.

The GW approximation is very promising for an accurate first-principles description of charged excitations in single-molecule-metal interfaces. In the cluster approach for electronic transport across molecules, the infinite metal (with an adsorbed molecule) is replaced by a finite cluster whose volume should be incrementally increased to test the approach to the thermodynamic limit. Here we show that in GW, the approach to the thermodynamic limit will be much slower than in Kohn-Sham density-functional theory (DFT) because of the Coulomb interaction. To demonstrate this statement, we investigate spectral gaps in an ensemble of disordered sodium clusters in Kohn-Sham DFT, quasiparticle eigenvalue-self-consistent GW and Hartree-Fock. The fundamental gaps (i.e. difference between the lowest unoccupied and highest occupied level) in GW scale as N-1/3 on average, where N is the number of atoms. We demonstrate that this slow decrease artificially depletes the density of states at the Fermi level when the cluster is used to simulate a semi-infinite electrode. Therefore, the GW method cannot be taken as an out-of-the-box improvement of the DFT in cluster geometries, unless careful convergence checks are performed.

Resonant transport in a highly conducting single molecular junction via metal-metal covalent bond.

Achieving highly transmitting molecular junctions through resonant transport at low bias is key to the next-generation low-power molecular devices. Although resonant transport in molecular junctions was observed by connecting a molecule between the metal electrodes via chemical anchors by applying a high source-drain bias (>1 V), the conductance was limited to <0.1G0, G0 being the quantum of conductance. Herein, we report electronic transport measurements by directly connecting a ferrocene molecule between Au electrodes under ambient conditions in a mechanically controllable break junction setup (MCBJ), revealing a conductance peak at ∼0.2G0 in the conductance histogram. A similar experiment was repeated for ferrocene terminated with amine (-NH2) and cyano (-CN) anchors, where conductance histograms exhibit an extended low conductance feature, including the sharp high conductance peak, similar to pristine ferrocene. The statistical analysis of the data and density functional theory-based transport calculation suggest a possible molecular conformation with a strong hybridization between the Au electrodes, and that the Fe atom of ferrocene is responsible for a near-perfect transmission in the vicinity of the Fermi energy, leading to the resonant transport at a small applied bias (<0.5 V). Moreover, calculations including van der Waals/dispersion corrections reveal a covalent-like organometallic bonding between Au and the central Fe atom of ferrocene, having bond energies of ∼660 meV. Overall, our study not only demonstrates the realization of an air-stable highly transmitting molecular junction, but also provides important insights about the nature of chemical bonding at the metal/organo-metallic interface.

Chirality-controlled spin scattering through quantum interference.

Chirality-induced spin selectivity has been reported in many experiments, but a generally accepted theoretical explanation has not yet been proposed. Here, we introduce a simple model system of a straight cylindrical free-electron wire containing a helical string of atomic scattering centers with spin-orbit interaction. The advantage of this simple model is that it allows deriving analytical expressions for the spin scattering rates, such that the origin of the effect can be easily followed. We find that spin-selective scattering can be viewed as resulting from the constructive interference of partial waves scattered by the spin-orbit terms. We demonstrate that forward scattering rates are independent of spin, while back scattering is spin dependent over wide windows of energy. Although the model does not represent the full details of electron transmission through chiral molecules, it clearly reveals a mechanism that could operate in chiral systems.

Current-induced mechanical torque in chiral molecular rotors.

There has been great endeavor to engineer molecular rotors operated by an electrical current. A frequently met operation principle is the transfer of angular momentum taken from the incident flux. In this paper, we present an alternative driving agent that works also in situations where angular momentum of the incoming flux is conserved. This situation arises typically with molecular rotors that exhibit an easy axis of rotation. For quantitative analysis we investigate here a classical model where molecule and wires are represented by a rigid curved path. We demonstrate that in the presence of chirality, the rotor generically undergoes a directed motion, provided that the incident current exceeds a threshold value. Above this threshold, the corresponding rotation frequency (per incoming particle current) for helical geometries turns out to be 2πm/M1, where m/M1 is the ratio of the mass of an incident charge carrier and the mass of the helix per winding number.

Structural Regulation of Mechanical Gating in Molecular Junctions.

In contrast to silicon-based transistors, single-molecule junctions can be gated by simple mechanical means. Specifically, charge can be transferred between the junction's electrodes and its molecular bridge when the interelectrode distance is modified, leading to variations in the electronic transport properties of the junction. While this effect has been studied extensively, the influence of the molecular orientation on mechanical gating has not been addressed, despite its potential influence on the gating effectiveness. Here, we show that the same molecular junction can experience either clear mechanical gating or none, depending on the molecular orientation in the junctions. The effect is found in silver-ferrocene-silver break junctions and analyzed in view of ab initio and transport calculations, where the influence of the molecular orbital geometry on charge transfer to or from the molecule is revealed. The molecular orientation is thus a new degree of freedom that can be used to optimize mechanically gated molecular junctions.

Chiral Light Emission from a Hybrid Magnetic Molecule-Monolayer Transition Metal Dichalcogenide Heterostructure.

Hybrid layered materials assembled from atomically thin crystals and small molecules bring great promises in pushing the current information and quantum technologies beyond the frontiers. We demonstrate here a class of layered valley-spin hybrid (VSH) materials composed of a monolayer two-dimensional (2D) semiconductor and double-decker single molecule magnets (SMMs). We have materialized a VSH prototype by thermal evaporation of terbium bis-phthalocyanine onto a MoS2 monolayer and revealed its composition and stability by both microscopic and spectroscopic probes. The interaction of the VSH components gives rise to the intersystem crossing of the photogenerated carriers and moderate p-doping of the MoS2 monolayer, as corroborated by the density functional theory calculations. We further explored the valley contrast by helicity-resolved photoluminescence (PL) microspectroscopy carried out down to liquid helium temperatures and in the presence of the external magnetic field. The most striking feature of the VSH is the enhanced A exciton-related valley emission observed at the out-of-resonance condition at room temperature, which we elucidated by the proposed nonradiative energy drain transfer mechanism. Our study thus demonstrates the experimental feasibility and great promises of the ultrathin VSH materials with chiral light emission, operable by physical fields for emerging opto-spintronic, valleytronic, and quantum information concepts.

Resolving Ambiguity of the Kondo Temperature Determination in Mechanically Tunable Single-Molecule Kondo Systems.

Determination of the molecular Kondo temperature (TK) poses a challenge in most cases when the experimental temperature cannot be tuned to a sufficient extent. We show how this ambiguity can be resolved if additional control parameters are present, such as magnetic field and mechanical gating. We record the evolution of the differential conductance by lifting an individual molecule from the metal surface with the tip of a scanning tunneling microscope. By fitting the measured conductance spectra with the single impurity Anderson model we are able to demonstrate that the lifting tunes the junction continuously from the strongly correlated Kondo-singlet to the free spin-1/2 ground state. In the crossover regime, where TK is similar to the temperature of experiment, the fitting yields ambiguous estimates of TK varying by an order of magnitude. We show that analysis of the conductance measured in two distinct external magnetic fields can be used to resolve this problem.

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.

Real space manifestations of coherent screening in atomic scale Kondo lattices.

The interaction among magnetic moments screened by conduction electrons drives quantum phase transitions between magnetically ordered and heavy-fermion ground states. Here, starting from isolated magnetic impurities in the Kondo regime, we investigate the formation of the finite size analogue of a heavy Fermi liquid. We build regularly-spaced chains of Co adatoms on a metallic surface by atomic manipulation. Scanning tunneling spectroscopy is used to obtain maps of the Kondo resonance intensity with sub-atomic resolution. For sufficiently small interatomic separation, the spatial distribution of Kondo screening does not coincide with the position of the adatoms. It also develops enhancements at both edges of the chains. Since we can rule out any other interaction between Kondo impurities, this is explained in terms of the indirect hybridization of the Kondo orbitals mediated by a coherent electron gas, the mechanism that causes the emergence of heavy quasiparticles in the thermodynamic limit.

Silver Makes Better Electrical Contacts to Thiol-Terminated Silanes than Gold.

We report that the single-molecule junction conductance of thiol-terminated silanes with Ag electrodes are higher than the conductance of those formed with Au electrodes. These results are in contrast to the trends in the metal work function Φ(Ag)<Φ(Au). As such, a better alignment of the Au Fermi level to the molecular orbital of silane that mediates charge transport would be expected. This conductance trend is reversed when we replace the thiols with amines, highlighting the impact of metal-S covalent and metal-NH2 dative bonds in controlling the molecular conductance. Density functional theory calculations elucidate the crucial role of the chemical linkers in determining the level alignment when molecules are attached to different metal contacts. We also demonstrate that conductance of thiol-terminated silanes with Pt electrodes is lower than the ones formed with Au and Ag electrodes, again in contrast to the trends in the metal work-functions.

Impact of Electrode Density of States on Transport through Pyridine-Linked Single Molecule Junctions.

We study the impact of electrode band structure on transport through single-molecule junctions by measuring the conductance of pyridine-based molecules using Ag and Au electrodes. Our experiments are carried out using the scanning tunneling microscope based break-junction technique and are supported by density functional theory based calculations. We find from both experiments and calculations that the coupling of the dominant transport orbital to the metal is stronger for Au-based junctions when compared with Ag-based junctions. We attribute this difference to relativistic effects, which result in an enhanced density of d-states at the Fermi energy for Au compared with Ag. We further show that the alignment of the conducting orbital relative to the Fermi level does not follow the work function difference between two metals and is different for conjugated and saturated systems. We thus demonstrate that the details of the molecular level alignment and electronic coupling in metal-organic interfaces do not follow simple rules but are rather the consequence of subtle local interactions.

Signature of the Dirac cone in the properties of linear oligoacenes.

Organic electronics offers prospects of functionality for science, industry and medicine that are new as compared with silicon technology and available at a very low material cost. Among the plethora of organic molecules available for materials design, polymers and oligomers are very promising, for example, because of their mechanical flexibility. They consist of repeated basic units, such as benzene rings, and the number of these units N determines their excitation gap, a property that is often used in proposals of organic photovoltaics. Here, we show that contrary to a widely held belief the magnitudes of excitation gaps do not always decay monotonously with N, but can oscillate due to the presence of a 'Dirac cone' in the band structure. With an eye on the more fundamental question how a molecular wire becomes metallic with increasing length, our research suggests that the process can exhibit incommensurate oscillations.

Atomically wired molecular junctions: connecting a single organic molecule by chains of metal atoms.

Using a break junction technique, we find a clear signature for the formation of conducting hybrid junctions composed of a single organic molecule (benzene, naphthalene, or anthracene) connected to chains of platinum atoms. The hybrid junctions exhibit metallic-like conductance (~0.1-1G0), which is rather insensitive to further elongation by additional atoms. At low bias voltage the hybrid junctions can be elongated significantly beyond the length of the bare atomic chains. Ab initio calculations reveal that benzene based hybrid junctions have a significant binding energy and high structural flexibility that may contribute to the survival of the hybrid junction during the elongation process. The fabrication of hybrid junctions opens the way for combining the different properties of atomic chains and organic molecules to realize a new class of atomic scale interfaces.

Multi-orbital non-crossing approximation from maximally localized Wannier functions: the Kondo signature of copper phthalocyanine on Ag(100).

We have developed a multi-orbital approach to compute the electronic structure of a quantum impurity using the non-crossing approximation. The calculation starts with a mean-field evaluation of the system's electronic structure using a standard quantum chemistry code; here we use density functional theory (DFT). We transformed the one-electron structure into an impurity Hamiltonian by using maximally localized Wannier functions. Hence, we have developed a method to study the Kondo effect in systems based on an initial one-electron calculation. We have applied our methodology to a copper phthalocyanine molecule chemisorbed on Ag(100), and we have described its spectral function for three different cases where the molecule presents a single spin or two spins with ferro- and anti-ferromagnetic exchange couplings. We find that the use of broken-symmetry mean-field theories such as Kohn-Sham DFT cannot deal with the complexity of the spin of open-shell molecules on metal surfaces and extra modeling is needed.

Band selection and disentanglement using maximally localized Wannier functions: the cases of Co impurities in bulk copper and the Cu(111) surface.

We have adapted the maximally localized Wannier function approach of Souza et al (2002 Phys. Rev. B 65 035109) to the density functional theory based SIESTA code (Soler et al 2002 J. Phys.: Condens. Mater. 14 2745) and applied it to the study of Co substitutional impurities in bulk copper as well as to the Cu(111) surface. In the Co impurity case, we have reduced the problem to the Co d-electrons and the Cu sp-band, permitting us to obtain an Anderson-like Hamiltonian from well defined density functional parameters in a fully orthonormal basis set. In order to test the quality of the Wannier approach to surfaces, we have studied the electronic structure of the Cu(111) surface by again transforming the density functional problem into the Wannier representation. An excellent description of the Shockley surface state is attained, permitting us to be confident in the application of this method to future studies of magnetic adsorbates in the presence of an extended surface state.