Abstract:
Platinum monatomic nanowires were predicted to spontaneously develop magnetism, involving a sizable orbital moment via spin orbit coupling, and a colossal magnetic anisotropy. We present here a fully-relativistic (spin-orbit coupling included) pseudo-potential density functional calculation of electronic and magnetic properties, and of Landauer ballistic conductance of Pt model nanocontacts consisting of short nanowire segments suspended between Pt leads or tips, reprented by bulk planes. Even if short, and despite the nonmagnetic Pt leads, the nanocontact is found to be locally magnetic with magnetization strictly parallel to its axis. Especially under strain, the energy barrier to flip the overall spin direction is predicted to be tens of meV high, and thus the corresponding blocking temperatures large, suggesting the use of static Landauer ballistic electrical conductance calculations. We carry out such calculations, to find that inclusion of spin-orbit coupling and of magnetism lowers the ballistic conductance by about $15\div20$% relative to the nonmagnetic case, yielding $ G\sim 2 G_0$ ($G_0=2e^2/h$), in good agreement with break junction results. The spin filtering properties of this highly unusual spontaneously magnetic nanocontact are also analysed.

Abstract:
CO adsorption on an Au monatomic chain is studied within density functional theory in nanocontact geometries as a function of the contact stretching. We compare the bridge and atop adsorption sites of CO, finding that the bridge site is energetically favored at all strains studied here. Atop adsorption gives rise to an almost complete suppression of the ballistic conductance of the nanocontact, while adsorption at the bridge site results in a conductance value close to 0.6 G0, in agreement with previous experimental data. We show that only the bridge site can qualitatively account for the evolution of the conductance as a function of the contact stretching observed in the experimental conductance traces. The numerical discrepancy between the theoretical and experimental conductance slopes is rationalized through a simple model for the elastic response of the metallic leads. We also verify that our conductance values are not affected by the specific choice of the nanocontact geometry by comparing two different atomistic models for the tips.

Abstract:
We study the energetics, the electronic structure, and the ballistic transport of an infinite Au monatomic chain with an adsorbed CO molecule. We find that the bridge adsorption site is energetically favored with respect to the atop site, both at the equilibrium Au-Au spacing of the chain and at larger spacings. Instead, a substitutional configuration requires a very elongated Au-Au bond, well above the rupture distance of the pristine Au chain. The electronic structure properties can be described by the Blyholder model, which involves the formation of bonding/antibonding pairs of 5{\sigma} and 2{\pi}* states through the hybridization between molecular levels of CO and metallic states of the chain. In the atop geometry, we find an almost vanishing conductance due to the 5{\sigma} antibonding states giving rise to a Fano-like destructive interference close to the Fermi energy. In the bridge geometry, instead, the same states are shifted to higher energies and the conductance reduction with respect to pristine Au chain is much smaller. We also examine the effects of strain on the ballistic transport, finding opposite behaviors for the atop and bridge conductances. Only the bridge geometry shows a strain dependence compatible with the experimental conductance traces.

Abstract:
The electrical conductance of atomic metal contacts represents a powerful tool to detect nanomagnetism. Conductance reflects magnetism through anomalies at zero bias -- generally with Fano lineshapes -- due to the Kondo screening of the magnetic impurity bridging the contact. A full atomic-level understanding of this nutshell many-body system is of the greatest importance, especially in view of our increasing need to control nanocurrents by means of magnetism. Disappointingly, zero bias conductance anomalies are not presently calculable from atomistic scratch. In this Letter we demonstrate a working route connecting approximately but quantitatively density functional theory (DFT) and numerical renormalization group (NRG) approaches and leading to a first-principles conductance calculation for a nanocontact, exemplified by a Ni impurity in a Au nanowire. A Fano-like conductance lineshape is obtained microscopically, and shown to be controlled by the impurity s-level position. We also find a relationship between conductance anomaly and geometry, and uncover the possibility of opposite antiferromagnetic and ferromagnetic Kondo screening -- the latter exhibiting a totally different and unexplored zero bias anomaly. The present matching method between DFT and NRG should permit the quantitative understanding and exploration of this larger variety of Kondo phenomena at more general magnetic nanocontacts.

Abstract:
We report tight-binding (TB) calculations of magnetocrystalline anisotropy energy (MAE) of Iron slabs and nanoclusters with a particuler focus on local analysis. After clarifying various concepts and formulations for the determination of MAE, we apply our realistic TB model to the analysis of the magnetic anisotropy of Fe$(001)$, Fe$(110)$ slabs and of two large Fe clusters with $(001)$ and $(110)$ facets only: a truncated pyramid and a truncated bipyramid containg 620 and 1096 atoms, respectively. It is shown that the MAE of slabs originates mainly from outer layers, a small contribution from the bulk gives rise, however, to an oscillatory behavior for large thicknesses. Interestingly, the MAE of the nanoclusters considered is almost solely due to $(001)$ facets and the base perimeter of the pyramid. We believe that this fact could be used to efficiently control the anisotropy of Iron nanoparticles and could also have consequences on their spin dynamics.

Abstract:
The complex band structure of an isolated polyethylene chain is calculated within Density Functional Theory (DFT). A plane wave basis and ultrasoft pseudopotentials are used. The results are compared with those obtained via a local basis set. We obtain a gap between the highest occupied molecular orbilar (HOMO) and the antibonding unoccupied molecular orbitals of 9.3 eV and a non-resonant tunneling $\beta$ parameter of 0.9 per monomer, in reasonable agreement with experiment and with results obtained via local basis. Polyethylene is a negative electron affinity material and the actual gap should be the energy of the HOMO with respect to the vacuum level (in DFT approximation only about 5.14 eV). The Bloch states at imaginary k are mainly free-electron-like parabolic bands which are missing in the local basis. We present also the complex bands of the bulk polyethylene in order to estimate the effects of the chain-chain interactions on the complex band structure. The relevance of these results for the tunnelling conduction of n-alkane chains is discussed.

Abstract:
Pt is known to show spontaneous formation of monatomic chains upon breaking a metallic contact. From model calculations, these chains are expected to be spin polarized. However, direct experimental evidence for or against magnetism is lacking. Here, we investigate shot noise as a potential source of information on the magnetic state of Pt atomic chains. We observe a remarkable structure in the distribution of measured shot-noise levels, where the data appear to be confined to the region of nonmagnetic states. While this suggests a nonmagnetic ground state for the Pt atomic chains, from calculations we find that the magnetism in Pt chains is due to 'actor' electron channels, which contribute very little to ballistic conductance and noise. On the other hand, there are weakly polarized 'spectator' channels, which carry most of the current and are only slightly modified by the magnetic state.

Abstract:
Molecular contacts are generally poorly conducting because their energy levels tend to lie far from the Fermi energy of the metal contact, necessitating undesirably large gate and bias voltages in molecular electronics applications. Molecular radicals are an exception because their partly filled orbitals undergo Kondo screening, opening the way to electron passage even at zero bias. While that phenomenon has been experimentally demonstrated for several complex organic radicals, quantitative theoretical predictions have not been attempted so far. It is therefore an open question whether and to what extent an ab initio-based theory is able to make accurate predictions for Kondo temperatures and conductance lineshapes. Choosing nitric oxide NO as a simple and exemplary spin 1/2 molecular radical, we present calculations based on a combination of density functional theory and numerical renormalization group (DFT+NRG) predicting a zero bias spectral anomaly with a Kondo temperature of 15 K for NO/Au(111). A scanning tunneling spectroscopy study is subsequently carried out to verify the prediction, and a striking zero bias Kondo anomaly is confirmed, still quite visible at liquid nitrogen temperatures. Comparison shows that the experimental Kondo temperature of about 43 K is larger than the theoretical one, while the inverted Fano lineshape implies a strong source of interference not included in the model. These discrepancies are not a surprise, providing in fact an instructive measure of the approximations used in the modeling, which supports and qualifies the viability of the DFT+NRG approach to the prediction of conductance anomalies in larger molecular radicals.

Abstract:
We report tight-binding (TB) and Density Function Theory (DFT) calculations of magnetocrystalline anisotropy energy (MAE) of free Fe (body centerd cubic) and Co (face centered cubic) slabs and nanocrystals. The nanocrystals are truncated square pyramids which can be obtained experimentally by deposition of metal on a SrTiO$_3$(001) substrate. For both elements our local analysis shows that the total MAE of the nanocrystals is largely dominated by the contribution of (001) facets. However, while the easy axis of Fe(001) is out-of-plane, it is in-plane for Co(001). This has direct consequences on the magnetic reversal mechanism of the nanocrystals. Indeed, the very high uniaxial anisotropy of Fe nanocrystals makes them a much better potential candidate for magnetic storage devices.

Abstract:
Spin-filter tunneling is a promising way to generate highly spin-polarized current, a key component for spintronics applications. In this work we explore the tunneling conductance across the spin-filter material CoFe2O4 interfaced with Au electrodes, a geometry which provides nearly perfect lattice matching at the CoFe2O4/Au(001) interface. Using density functional theory calculations we demonstrate that interface states play a decisive role in controlling the transport spin polarization in this tunnel junction. For a realistic CoFe2O4 barrier thickness, we predict a tunneling spin polarization of about -60%. We show that this value is lower than what is expected based solely on considerations of the spin-polarized band structure of CoFe2O4, and therefore that these interface states can play a detrimental role. We argue this is a rather general feature of ferrimagnetic ferrites and could make an important impact on spin-filter tunneling applications.