Robust nanotube-based nanosensor designed for the detection of explosive molecules.

The adequate determination and detection of explosive molecules is key to introducing improvements in areas related to safety, whose progress depends on an adequate and rapid determination of dangerous substances. To detect explosives down to the molecular level and accurately discriminate between different but somehow similar substances, it is necessary to design sensors that can differentiate them uniquely and efficiently. In this study, we present a new generation nanoscale sensor based on carbon nanotubes with an adapted nanopore shape that is capable of effectively discriminating between five types of explosive compounds (TATP, RDX, PENT, HMX and DNT).

Selective Sensing of DNA Nucleobases with Angular Discrimination.

The fast and precise selective sensing of DNA nucleobases is a long-pursued method that can lead to huge advances in the field of genomics and have an impact on aspects such as the prevention of diseases, health enhancement, and, in general, all types of medical treatments. We present here a new type of nanoscale sensor based on carbon nanotubes with a specific geometry that can discriminate the type of nucleobase and also its angle of orientation. The proper differentiation of nucleobases is essential to clearly sequence DNA chains, while angular discrimination is key to improving the sensing selectivity.

Towards nanotube-based sensors for discrimination of drug molecules.

The proper detection of drug molecules is key for applications that have an impact in several fields, ranging from medical treatments to industrial applications. In case of illegal drugs, their correct and fast detection has important implications that affect different parts of society such as security or public health. Here we present a method based on nanoscale sensors made of carbon nanotubes modified with dopants that can detect three types of drug molecules: mephedrone, methamphetamine and heroin.

Thermoelectric Response Enhanced by Surface/Edge States in Physical Nanogaps.

Current solid-state thermoelectric converters have poor performance, which typically renders them useless for practical applications. This problem is evidenced by the small figures of merit of typical thermoelectric materials, which tend to be much smaller than 1. Increasing this parameter is then key for the development of functional devices in technologically viable applications that can work optimally.

Effect of Impurity Adsorption on the Electronic and Transport Properties of Graphene Nanogaps.

Graphene stands out as a versatile material with several uses in fields that range from electronics to biology. In particular, graphene has been proposed as an electrode in molecular electronics devices that are expected to be more stable and reproducible than typical ones based on metallic electrodes. In this work, we study by means of first principles, simulations and a tight-binding model the electronic and transport properties of graphene nanogaps with straight edges and different passivating atoms: Hydrogen or elements of the second row of the periodic table (boron, carbon, nitrogen, oxygen, and fluoride).

The CECAM electronic structure library and the modular software development paradigm.

First-principles electronic structure calculations are now accessible to a very large community of users across many disciplines, thanks to many successful software packages, some of which are described in this special issue. The traditional coding paradigm for such packages is monolithic, i.e.

Dynamically Stable Topological Phase of Arsenene.

First-principles calculations based on density functional theory (DFT) are used to investigate the electronic structures and topological phase transition of arsenene under tensile and compressive strains. Buckling in arsenene strongly depends on compressive/tensile strain. The phonons band structures reveal that arsenene is dynamically stable up to 18% tensile strain and the frequency gap between the optical and acoustic branches decreases with strain.

Modelling and evaluation of PEM hydrogen technologies for frequency ancillary services in future multi-energy sustainable power systems.

This paper examines the prospect of PEM (Proton Exchange Membrane) electrolyzers and fuel cells to partake in European electrical ancillary services markets. First, the current framework of ancillary services is reviewed and discussed, emphasizing the ongoing European harmonization plans for future frequency balancing markets. Next, the technical characteristics of PEM hydrogen technologies and their potential uses within the electrical power system are discussed to evaluate their adequacy to the requirements of ancillary services markets.

In-situ formation of one-dimensional coordination polymers in molecular junctions.

We demonstrate the bottom-up in-situ formation of organometallic oligomer chains at the single-molecule level. The chains are formed using the mechanically controllable break junction technique operated in a liquid environment, and consist of alternating isocyano-terminated benzene monomers coordinated to gold atoms. We show that the chaining process is critically determined by the surface density of molecules.

Spin signatures in the electrical response of graphene nanogaps.

We analyse the electrical response of narrow graphene nanogaps in search for transport signatures stemming from spin-polarized edge states. We find that the electrical transport across graphene nanogaps having perfectly defined zigzag edges does not carry any spin-related signature. We also analyse the magnetic and electrical properties of nanogaps whose electrodes have wedges that possibly occur in the currently fabricated nanogaps.

Mechanically controlled quantum interference in graphene break junctions.

The ability to detect and distinguish quantum interference signatures is important for both fundamental research and for the realization of devices such as electron resonators, interferometers and interference-based spin filters. Consistent with the principles of subwavelength optics, the wave nature of electrons can give rise to various types of interference effects, such as Fabry-Pérot resonances, Fano resonances and the Aharonov-Bohm effect. Quantum interference conductance oscillations have, indeed, been predicted for multiwall carbon nanotube shuttles and telescopes, and arise from atomic-scale displacements between the inner and outer tubes.

Multifunctional nanostructured Co-doped ZnO: Co spatial distribution and correlated magnetic properties.

In this report we present a systematic structural and magnetic analysis of Co-doped ZnO nanoparticles prepared via a microwave-assisted hydrothermal route. The structural data confirm the incorporation of Co ions into the wurtzite ZnO lattice and a Co concentration mainly near/at the surface of the nanoparticles. This Co spatial distribution is set to passivate the surface of the ZnO nanoparticles, inhibiting the nanoparticle growth and suppressing the observation of a ferromagnetic phase.

Spin-state dependent conductance switching in single molecule-graphene junctions.

Spin-crossover (SCO) molecules are versatile magnetic switches with applications in molecular electronics and spintronics. Downscaling devices to the single-molecule level remains, however, a challenging task since the switching mechanism in bulk is mediated by cooperative intermolecular interactions. Here, we report on electron transport through individual Fe-SCO molecules coupled to few-layer graphene electrodes via π-π stacking.

Thermoelectricity in vertical graphene-C-graphene architectures.

Recent studies of single-molecule thermoelectricity have identified families of high-performance molecules. However, in order to translate this discovery into practical thin-film energy-harvesting devices, there is a need for an understanding of the fundamental issues arising when such junctions are placed in parallel. This is relevant because controlled scalability might be used to boost electrical and thermoelectric performance over the current single-junction paradigm.

Synthesis and Single-Molecule Conductance Study of Redox-Active Ruthenium Complexes with Pyridyl and Dihydrobenzo[b]thiophene Anchoring Groups.

The ancillary ligands 4'-(4-pyridyl)-2,2':6',2''-terpyridine and 4'-(2,3-dihydrobenzo[b]thiophene)-2,2'-6',2"-terpyridine were used to synthesize two series of mono- and dinuclear ruthenium complexes differing in their lengths and anchoring groups. The electrochemical and single-molecular conductance properties of these two series of ruthenium complexes were studied experimentally by means of cyclic voltammetry and the scanning tunneling microscopy-break junction technique (STM-BJ) and theoretically by means of density functional theory (DFT). Cyclic voltammetry data showed clear redox peaks corresponding to both the metal- and ligand-related redox reactions.

Redox control of thermopower and figure of merit in phase-coherent molecular wires.

We demonstrate how redox control of intra-molecular quantum interference in phase-coherent molecular wires can be used to enhance the thermopower (Seebeck coefficient) S and thermoelectric figure of merit ZT of single molecules attached to nanogap electrodes. Using first principles theory, we study the thermoelectric properties of a family of nine molecules, which consist of dithiol-terminated oligo (phenylene-ethynylenes) (OPEs) containing various central units. Uniquely, one molecule of this family possesses a conjugated acene-based central backbone attached via triple bonds to terminal sulfur atoms bound to gold electrodes and incorporates a fully conjugated hydroquinonecentral unit.

Simplifying the conductance profiles of molecular junctions: the use of the trimethylsilylethynyl moiety as a molecule-gold contact.

Conductance across a metal|molecule|metal junction is strongly influenced by the molecule-substrate contacts, and for a given molecular structure, multiple conductance values are frequently observed and ascribed to distinct binding modes of the contact at each of the molecular termini. Conjugated molecules containing a trimethylsilylethynyl terminus, -C≡CSiMe(3) give exclusively a single conductance value in I(s) measurements on gold substrates, the value of which is similar to that observed for the same molecular backbone with thiol and amine based contacting groups when bound to under-coordinated surface sites.

Correlations between molecular structure and single-junction conductance: a case study with oligo(phenylene-ethynylene)-type wires.

The charge transport characteristics of 11 tailor-made dithiol-terminated oligo(phenylene-ethynylene) (OPE)-type molecules attached to two gold electrodes were studied at a solid/liquid interface in a combined approach using an STM break junction (STM-BJ) and a mechanically controlled break junction (MCBJ) setup. We designed and characterized 11 structurally distinct dithiol-terminated OPE-type molecules with varied length and HOMO/LUMO energy. Increase of the molecular length and/or of the HOMO-LUMO gap leads to a decrease of the single-junction conductance of the linearly conjugate acenes.

Long-range electron tunnelling in oligo-porphyrin molecular wires.

Short chains of porphyrin molecules can mediate electron transport over distances as long as 5-10 nm with low attenuation. This means that porphyrin-based molecular wires could be useful in nanoelectronic and photovoltaic devices, but the mechanisms responsible for charge transport in single oligo-porphyrin wires have not yet been established. Here, based on electrical measurements of single-molecule junctions, we show that the conductance of the oligo-porphyrin wires has a strong dependence on temperature, and a weak dependence on the length of the wire.

Oligoyne single molecule wires.

We report the electrical conductance at the single molecule level of the oligoyne molecular wires Py-(C[triple bond]C)(n)-Py (n = 1, 2 and 4; Py = 4-pyridyl) using STM-molecular break junction techniques in Au|molecule|Au configurations. The conductance histograms reveal multiple series of peaks attributed to differing contact geometries between the pyridyl head groups and the gold electrodes. Both experimental and theoretical evidence point to the higher conduction groups being related to adsorption of the pyridyl group at more highly coordinated sites such as step edges or alongside gold adatoms.

First-principles study of electron transport through the single-molecule magnet Mn12.

We examine electron transport through a single-molecule magnet Mn(12) bridged between Au electrodes using the first-principles method. We find crucial features which were inaccessible in model Hamiltonian studies: spin filtering and a strong dependence of charge distribution on local environments. The spin filtering remains robust with different molecular geometries and interfaces, and strong electron correlations, while the charge distribution over the Mn(12) strongly depends on them.

Adverse effects of asymmetric contacts on single molecule conductances of HS(CH2)n COOH in nanoelectrical junctions.

A scanning tunnelling microscope has been used to determine the conductance of single molecular wires with the configuration X-bridge-X, X-bridge-Y and Y-bridge-Y (X = thiol terminus and Y = COOH). We find that for molecular wires with mixed functional groups (X-bridge-Y) the single molecule conductance decreases with respect to the comparable symmetric molecules. These differences are confirmed by theoretical computations based on a combination of density functional theory and the non-equilibrium Green's functions formalism.

Tuning the electrical conductivity of nanotube-encapsulated metallocene wires.

We analyze a new family of carbon nanotube-based molecular wires, formed by encapsulating metallocene molecules inside the nanotubes. Our simulations, which are based on a combination of nonequilibrium Green function techniques and density functional theory, indicate that these wires can be engineered to exhibit desirable magnetotransport effects for use in spintronics devices. The proposed structures should also be resilient to room-temperature fluctuations, and are expected to have a high yield.

Towards molecular spintronics.

The ability to manipulate electron spin in organic molecular materials offers a new and extremely tantalizing route towards spin electronics, both from fundamental and technological points of view. This is mainly due to the unquestionable advantage of weak spin-orbit and hyperfine interactions in organic molecules, which leads to the possibility of preserving spin-coherence over times and distances much longer than in conventional metals or semiconductors. Here we demonstrate theoretically that organic spin valves, obtained by sandwiching an organic molecule between magnetic contacts, can show a large bias-dependent magnetoresistance and that this can be engineered by an appropriate choice of molecules and anchoring groups.