arXiv subjects

D. Jacob

Publications and source records attributed to D. Jacob.

At least 19 recordsLinked to original sources

arXiv2023

Beyond spin models in orbitally-degenerate open-shell nanographenes

The study of open-shell nanographenes has relied on a paradigm where spins are the only low-energy degrees of freedom. Here we show that some nanographenes can host low-energy excitations that include strongly coupled spin and orbital degrees of freedom. The key ingredient is the existence of orbital degeneracy, as a consequence of leaving the benzenoid/half-filling scenario. We analyze the case of nitrogen-doped triangulenes, using both density-functional theory and Hubbard model multiconfigurational and random-phase approximation calculations. We find a rich interplay between orbital and spin degrees of freedom that confirms the need to go beyond the spin-only paradigm, opening a new venue in this field of research.

cond-mat.mes-hall↗

arXiv2023

Exchange interactions and intermolecular hybridization in a spin-1/2 nanographene dimer

Phenalenyl is a radical nanographene with triangular shape that hosts an unpaired electron with spin S = 1/2. The open-shell nature of phenalenyl is expected to be retained in covalently bonded networks. Here, we study a first step in that direction and report the synthesis of the phenalenyl dimer by combining in-solution synthesis and on-surface activation and its characterization both on Au(111) and on a monolayer of NaCl on top of Au(111) by means of inelastic electron tunneling spectroscopy (IETS). IETS shows inelastic steps that, together with a thorough theoretical analysis, are identified as the singlet-triplet excitation arising from interphenalenyl exchange. Two prominent features of our data permit to shed light on the nature of spin interactions in this system. First, the excitation energies with and without the NaCl decoupling layer are 48 and 41 meV, respectively, indicating a significant renormalization of the spin excitation energies due to exchange with the Au(111) electrons. Second, a position-dependent bias-asymmetry of the height of the inelastic steps is accounted for by an interphenalenyl hybridization of the singly occupied phenalenyl orbitals that is only possible via third neighbor hopping. This hybridization is also essential to activate kinetic interphenalenyl exchange. Our results set the stage for future work on the bottom-up synthesis of spin S = 1/2 spin lattices with large exchange interaction.

cond-mat.mes-hall↗

arXiv2018

On the origin of the quasi-particle peak in Cr(001) surfaces

In the spectral density of Cr(001) surfaces a sharp resonance close to the Fermi level is observed in both experiment and theory. For the physical origin of this peak two mechanisms were proposed. A single particle dz2 surface state renormalised by electron-phonon coupling and an orbital Kondo effect due to the degenerate dxz/dyz states. Despite several experimental and theoretical investigations, the origin is still under debate. In this work we address this problem by two different approaches of the dynamical mean-field theory. First, by the spin-polarized T-matrix fluctuation exchange approximation suitable for weakly and moderately correlated systems. Second, by the non-crossing approximation derived in the limit of weak hybridization (i.e. for strongly correlated systems) capturing Kondo-like processes. By using recent continuous-time quantum Monte Carlo calculations as a benchmark, we find that the high-energy features, everything except the resonance, of the spectrum is captured within the spin-polarized T-matrix fluctuation exchange approximation. More precisely the particle-particle processes provide the main contribution. For the non-crossing approximation it appears that spin-polarized calculations suffer from spurious behavior at the Fermi level. Then, we turned to non spin-polarized calculations to avoid this unphysical behavior. By employing two plausible starting hybridization functions, it is observed that the characteristics of the resonance are crucially dependent on the starting point. It appears that only one of these starting hybridizations could result in an orbital Kondo resonance in the presence of a strong magnetic field like in the Cr(001) surface. It is for a future investigation to first resolve the unphysical behavior within the spin-polarized non-crossing approximation and then check for an orbital Kondo resonance.

cond-mat.str-el↗

arXiv2017

Renormalization of single-ion magnetic anisotropy in the absence of Kondo effect

Inelastic spin flip excitations associated with single-ion magnetic anisotropy of quantum spins, can be strongly renormalized by Kondo exchange coupling to the conduction electrons in the substrate, as shown recently for the case of Co adatoms on CuN$_2$ islands. In this case differential conductance spectra show zero-bias anomalies due to a Kondo effect of the doubly degenerate ground state, and finite-bias step features due to spin flip excitations. Here I consider spin-1 quantum magnets with positive uniaxial anisotropy, where the ground state is non-degenerate and hence the Kondo effect does not take place. Nevertheless the renormalization of inelastic spin excitations due to exchange coupling by hybridization of the quantum spin with the conduction electrons still takes place despite the complete absence of the Kondo effect in the ground state. Additionally, I show that away from particle-hole symmetry, charge fluctuations have a similar effect to Kondo exchange coupling, leading to the renormalization of spin flip excitations. However, in contrast to the renormalization by Kondo exchange, charge fluctuations lead to asymmetric spectra, which for strong charge fluctuations can mimic Fano behavior.

cond-mat.mes-hall↗

arXiv2017

Anomalous magnetism in hydrogenated graphene

We revisit the problem of local moment formation in graphene due to chemisorption of individual atomic hydrogen or other analogous sp$^3$ covalent functionalizations. We describe graphene with the single orbital Hubbard model, so that the H chemisorption is equivalent to a vacancy in the honeycomb lattice. In order to circumvent artefacts related to periodic unit cells, we use either huge simulation cells of up to $8\times10^5$ sites, or an embedding scheme that allows the modelling of a single vacancy in an otherwise pristine infinite honeycomb lattice. We find three results that stress the anomalous nature of the magnetic moment ($m$) in this system. First, in the non-interacting ($U=0$), zero temperature ($T=0$) case, the $m(B)$ is a continuous smooth curve with divergent susceptibility, different from the step-wise constant function found for a single unpaired spins in a gapped system. Second, for $U=0$ and $T>0$, the linear susceptibility follows a power law $\propto{T}^{-\alpha}$ with an exponent of $\alpha=0.77$ different from conventional Curie's law. For $U>0$, in the mean field approximation, the integrated moment is smaller than $m=1\mu_B$, in contrast with results using periodic unit cells. These three results highlight that the magnetic response of the local moment induced by sp$^3$ functionalizations in graphene is different both from that of local moments in gaped systems, for which the magnetic moment is quantized and follows a Curie law, and from Pauli paramagnetism in conductors, for which a linear susceptibility can be defined at $T=0$.

cond-mat.mtrl-sci↗

arXiv2016

Kondo physics of the Anderson impurity model by Distributional Exact Diagonalization

The Distributional Exact Diagonalization (DED) scheme is applied to the description of Kondo physics in the Anderson impurity model. DED maps Anderson's problem of an interacting impurity level coupled to an infinite bath onto an ensemble of finite Anderson models, each of which can be solved by exact diagonalization. An approximation to the self-energy of the original infinite model is then obtained from the ensemble averaged self-energy. Using Friedel's sum rule, we show that the particle number constraint, a central ingredient of the DED scheme, ultimately imposes Fermi liquid behavior on the ensemble averaged self-energy, and thus is essential for the description of Kondo physics within DED. Using the Numerical Renormalization Group (NRG) method as a benchmark, we show that DED yields excellent spectra, both inside and outside the Kondo regime for a moderate number of bath sites. Only for very strong correlations ($U/\Gamma\gg10$) does the number of bath sites needed to achieve good quantitative agreement become too large to be computationally feasible.

cond-mat.str-el↗

arXiv2016

Effects of valence, geometry and electronic correlations on transport in transition metal benzene sandwich molecules

We study the impact of the valence and the geometry on the electronic structure and transport properties of different transition metal-benzene sandwich molecules bridging the tips of a Cu nanocontact. Our density-functional calculations show that the electronic transport properties of the molecules depend strongly on the molecular geometry which can be controlled by the nanocontact tips. Depending on the valence of the transition metal center certain molecules can be tuned in and out of half-metallic behaviour facilitating potential spintronics applications. We also discuss our results in the framework of an Anderson impurity model, indicating cases where the inclusion of local correlations alters the ground state qualitatively. For Co and V centered molecules we find indications of an orbital Kondo effect.

cond-mat.mes-hall↗

arXiv2015

Competition between quantum spin tunneling and Kondo effect

Quantum spin tunneling (QST) and Kondo effect are two very different quantum phenomena that produce the same effect on quantized spins, namely, the quenching of their magnetization. However, the nature of this quenching is very different so that QST and Kondo effects compete with each other. Importantly, both QST and Kondo produce very characteristic features in the spectral function that can be measured by means of single spin scanning tunneling spectroscopy that makes it possible to probe the crossover from one regime to the other. We model this crossover, and the resulting changes in transport, using a non-perturbative treatment of a generalized Anderson model including magnetic anisotropy that leads to quantum spin tunneling. We predict that, at zero magnetic field, integer spins can feature a split-Kondo peak driven by quantum spin tunneling.

cond-mat.mes-hall↗

arXiv2015

Towards a full ab initio theory of strong electronic correlations in nanoscale devices

In this paper I give a detailed account of an ab initio methodology for describing strong electronic correlations in nanoscale devices hosting transition metal atoms with open $d$- or $f$-shells. The method combines Kohn-Sham Density Functional Theory for treating the weakly interacting electrons on a static mean-field level with non-perturbative many-body methods for the strongly interacting electrons in the open $d$- and $f$-shells. An effective description of the strongly interacting electrons in terms of a multi-orbital Anderson impurity model is obtained by projection onto the strongly correlated subspace properly taking into account the non-orthogonality of the atomic basis set. A special focus lies on the ab initio calculation of the effective screened interaction matrix U for the Anderson model. Solution of the effective Anderson model with the One-Crossing approximation or other impurity solver techniques yields the dynamic correlations within the strongly correlated subspace giving rise e.g. to the Kondo effect. As an example the method is applied to the case of a Co adatom on the Cu(001) surface. The calculated low-bias tunnel spectra show Fano-Kondo lineshapes similar to those measured in experiments. The exact shape of the Fano-Kondo feature as well as its width depend quite strongly on the filling of the Co $3d$-shell. Although this somewhat hampers accurate quantitative predictions regarding lineshapes and Kondo temperatures, the overall physical situation can be predicted quite reliably.

cond-mat.mes-hall↗

arXiv2013

Kondo effect and spin quenching in high-spin molecules on metal substrates

Using a state-of-the art combination of density functional theory and impurity solver techniques we present a complete and parameter-free picture of the Kondo effect in the high-spin ($S=3/2$) coordination complex known as Manganese Phthalocyanine adsorbed on the Pb(111) surface. We calculate the correlated electronic structure and corresponding tunnel spectrum and find an asymmetric Kondo resonance, as recently observed in experiments. Contrary to previous claims, the Kondo resonance stems from only one of three possible Kondo channels with origin in the Mn 3d-orbitals, its peculiar asymmetric shape arising from the modulation of the hybridization due to strong coupling to the organic ligand. The spectral signature of the second Kondo channel is strongly suppressed as the screening occurs via the formation of a many-body singlet with the organic part of the molecule. Finally, a spin-1/2 in the 3d-shell remains completely unscreened due to the lack of hybridization of the corresponding orbital with the substrate, hence leading to a spin-3/2 underscreened Kondo effect.

cond-mat.mes-hall↗

arXiv2011

Orbital Kondo effect in Cobalt-Benzene sandwich molecules

We study a Co-benzene sandwich molecule bridging the tips of a Cu nanocontact as a realistic model of correlated molecular transport. To this end we employ a recently developed method for calculating the correlated electronic structure and transport properties of nanoscopic conductors. When the molecule is slightly compressed by the tips of the nanocontact the dynamic correlations originating from the strongly interacting Co 3d shell give rise to an orbital Kondo effect while the usual spin Kondo effect is suppressed due to Hund's rule coupling. This non-trivial Kondo effect produces a sharp and temperature-dependent Abrikosov-Suhl resonance in the spectral function at the Fermi level and a corresponding Fano line shape in the low bias conductance.

cond-mat.str-el↗

arXiv2010

Dynamical Mean-Field Theory for Molecular Electronics: Electronic Structure and Transport Properties

We present an approach for calculating the electronic structure and transport properties of nanoscopic conductors that takes into account the dynamical correlations of strongly interacting d- or f-electrons by combining density functional theory calculations with the dynamical mean-field theory. While the density functional calculation yields a static mean-field description of the weakly interacting electrons, the dynamical mean-field theory explicitly takes into account the dynamical correlations of the strongly interacting d- or f-electrons of transition metal atoms. As an example we calculate the electronic structure and conductance of Ni nanocontacts between Cu electrodes. We find that the dynamical correlations of the Ni 3d-electrons give rise to quasi-particle resonances at the Fermi-level in the spectral density. The quasi-particle resonances in turn lead to Fano lineshapes in the conductance characteristics of the nanocontacts similar to those measured in recent experiments of magnetic nanocontacts.

cond-mat.mes-hall↗

arXiv2010

Critical comparison of electrode models in density functional theory based quantum transport calculations

We study the performance of two different electrode models in quantum transport calculations based on density functional theory: Parametrized Bethe lattices and quasi-one dimensional wires or nanowires. A detailed account of implementation details in both cases is given. From the systematic study of nanocontacts made of representative metallic elements, we can conclude that parametrized electrode models represent an excellent compromise between computational cost and electronic structure definition as long as the aim is to compare with experiments where the precise atomic structure of the electrodes is not relevant or defined with precision. The results obtained using parametrized Bethe lattices are essentially similar to the ones obtained with quasi one dimensional electrodes for large enough sections of these, adding a natural smearing to the transmission curves that mimics the true nature of polycrystalline electrodes. The latter are more demanding from the computational point of view, but present the advantage of expanding the range of applicability of transport calculations to situations where the electrodes have a well-defined atomic structure, as is case for carbon nanotubes, graphene nanoribbons or semiconducting nanowires. All the analysis is done with the help of codes developed by the authors which can be found in the quantum transport toolbox Alacant and are publicly available.

cond-mat.mes-hall↗

arXiv2010

Orbital selective and tunable Kondo effect of magnetic adatoms on graphene: Correlated electronic structure calculations

We have studied the effect of dynamical correlations on the electronic structure of single Co adatoms on graphene monolayers with a recently developed novel method for nanoscopic materials that combines density functional calculations with a fully dynamical treatment of the strongly interacting 3d-electrons. The coupling of the Co 3d-shell to the graphene substrate and hence the dynamic correlations are strongly dependent on the orbital symmetry and the system parameters (temperature, distance of the adatom from the graphene sheet, gate voltage). When the Kondo effect takes place, we find that the dynamical correlations give rise to strongly temperature-dependent peaks in the Co 3d-spectra near the Fermi level. Moreover, we find that the Kondo effect can be tuned by the application of a gate voltage. It turns out that the position of the Kondo peaks is pinned to the Dirac points of graphene rather than to the chemical potential.

cond-mat.mes-hall↗

arXiv2009

The Kondo effect in ferromagnetic atomic contacts

Iron, cobalt and nickel are archetypal ferromagnetic metals. In bulk, electronic conduction in these materials takes place mainly through the $s$ and $p$ electrons, whereas the magnetic moments are mostly in the narrow $d$-electron bands, where they tend to align. This general picture may change at the nanoscale because electrons at the surfaces of materials experience interactions that differ from those in the bulk. Here we show direct evidence for such changes: electronic transport in atomic-scale contacts of pure ferromagnets (iron, cobalt and nickel), despite their strong bulk ferromagnetism, unexpectedly reveal Kondo physics, that is, the screening of local magnetic moments by the conduction electrons below a characteristic temperature. The Kondo effect creates a sharp resonance at the Fermi energy, affecting the electrical properties of the system;this appears as a Fano-Kondo resonance in the conductance characteristics as observed in other artificial nanostructures. The study of hundreds of contacts shows material-dependent lognormal distributions of the resonance width that arise naturally from Kondo theory. These resonances broaden and disappear with increasing temperature, also as in standard Kondo systems. Our observations, supported by calculations, imply that coordination changes can significantly modify magnetism at the nanoscale. Therefore, in addition to standard micromagnetic physics, strong electronic correlations along with atomic-scale geometry need to be considered when investigating the magnetic properties of magnetic nanostructures.

cond-mat.str-el↗

arXiv2009

Mechanical, Electrical, and Magnetic Properties of Ni Nanocontacts

The dynamic deformation upon stretching of Ni nanowires as those formed with mechanically controllable break junctions or with a scanning tunneling microscope is studied both experimentally and theoretically. Molecular dynamics simulations of the breaking process are performed. In addition, and in order to compare with experiments, we also compute the transport properties in the last stages before failure using the first-principles implementation of Landauer's formalism included in our transport package ALACANT.

cond-mat.mes-hall↗

arXiv2009

Kondo effect and conductance of nanocontacts with magnetic impurities

We study the impact of dynamical correlations on the electronic structure and coherent transport properties of Cu nanocontacts hosting a single magnetic impurity (Ni,Co,Fe) in the contact region. The strong dynamical correlations of the impurity 3d-electrons are fully taken into account by combining density functional calculations with a dynamical treatment of the impurity 3d-shell in the one-crossing approximation. We find that dynamical correlations give rise to the Kondo effect and lead to Fano features in the coherent transport characteristics similar to those observed in related experiments.

cond-mat.mes-hall↗

arXiv2008

Combining the Hybrid Functional Method with Dynamical Mean-Field Theory

We present a new method to compute the electronic structure of correlated materials combining the hybrid functional method with the dynamical mean-field theory. As a test example of the method we study cerium sesquioxide, a strongly correlated Mott-band insulator. The hybrid functional part improves the magnitude of the pd-band gap which is underestimated in the standard approximations to density functional theory while the dynamical mean-field theory part splits the 4f-electron spectra into a lower and an upper Hubbard band.

cond-mat.mtrl-sci↗