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Although iron-based catalysts are regarded as a promising alternative to precious metal catalysts, their precise electronic structures during catalysis still pose challenges for computational descriptions. A particularly urgent question is the influence of the environment on the electronic structure, and how to describe this properly with computational methods. Here, we study an iron porphyrin chloride complex adsorbed on a graphene sheet using density functional theory calculations to detail how much the electronic structure is influenced by the presence of a graphene layer. Our results indicate that weak interactions due to van der Waals forces dominate between the porphyrin complex and graphene, and only a small amount of charge is transferred between the two entities. Furthermore, the interplay of the ligand field environment, strong p − d hybridization, and correlation effects within the complex are strongly involved in determining the spin state of the iron ion. By bridging molecular chemistry and solid state physics, this study provides first steps towards a joint analysis of the properties of iron-based catalysts from first principles.
We use the topological heavy fermion (THF) model and its Kondo Lattice (KL) formulation to study the symmetric Kondo state in twisted bilayer graphene. Via a large-N approximation, we find a symmetric Kondo (SK) state in KL mode at fillings ν=0,±1,±2. In the SK state, all symmetries are preserved and the local moments are Kondo screened by the conduction electrons. At the mean-field level of the THF model at ν=0,±1,±2,±3, we also find a similar symmetric state. We study the stability of the symmetric state by comparing its energy with the ordered states and find the ordered states to have lower energy. However, moving away from integer fillings by doping holes to the light bands, we find the energy difference is reduced, which suggests the loss of ordering and a tendency towards Kondo screening. In order to include many-body effects beyond the mean-field approximation, we perform dynamical mean-field theory (DMFT) calculations on the THF model. We find the spin susceptibility follows a Curie behavior at ν=0,±1,±2 down to ∼2K where the onset of screening of the local moment becomes visible. This hints to very low Kondo temperatures at these fillings, in agreement with the outcome of our mean-field calculations. At non-integer filling ν=±0.5,±0.8,±1.2 DMFT shows deviations from a 1/T-susceptibility at much higher temperatures, suggesting a more effective screening of local moments with doping. Finally, we study the effect of a C3z-rotational-symmetry-breaking strain via mean-field approaches and find that a symmetric phase (that only breaks C3z symmetry) can be stabilized at sufficiently large strain at ν=0,±1,±2. Our results suggest that a symmetric Kondo phase is strongly suppressed at integer fillings, but could be stabilized either at non-integer fillings or by applying strain.
Motivated by the wealth of proposals and realizations of nontrivial topological phases in EuCd2As2, such as a Weyl semimetallic state and the recently discussed semimetallic versus semiconductor behavior in this system, we analyze in this work the role of the delicate interplay of Eu magnetism, strain and pressure on the realization of such phases. For that we invoke a combination of a group theoretical analysis with ab initio density functional theory calculations and uncover a rich phase diagram with various non-trivial topological phases beyond a Weyl semimetallic state, such as axion and topological crystalline insulating phases, and discuss their realization.
Motivated by the wealth of proposals and realizations of nontrivial topological phases in EuCd2As2, such as a Weyl semimetallic state and the recently discussed semimetallic versus semiconductor behavior in this system, we analyze in this work the role of the delicate interplay of Eu magnetism, strain and pressure on the realization of such phases. For that we invoke a combination of a group theoretical analysis with ab initio density functional theory calculations and uncover a rich phase diagram with various non-trivial topological phases beyond a Weyl semimetallic state, such as axion and topological crystalline insulating phases, and discuss their realization.
Under temperature or pressure tuning, tetragonal EuPd2Si2 is known to undergo a valence transition from nearly divalent to nearly trivalent Eu accompanied by a volume reduction. Albeit intensive work, its microscopic origin is still being discussed. Here, we investigate the mechanism of the valence transition under volume compression by ab initio density functional theory (DFT) calculations. Our analysis of the electronic and magnetic properties of EuPd2Si2 when approaching the valence transition shows an enhanced c-f hybridization between localized Eu 4f states and itinerant conduction states (Eu 5d, Pd 4d, and Si 3p) where an electronic charge redistribution takes place. We observe that the change in the electronic structure is intimately related to the volume reduction where Eu-Pd(Si) bond lengths shorten and, for the transition to happen, we trace the delicate balance between electronic bandwidth, crystal field splitting, Coulomb repulsion, Hund's coupling and spin-orbit coupling. In a next step we compare and benchmark our DFT results to surface-sensitive photoemission data in which the mixed-valent properties of EuPd2Si2 are reflected in a simultaneous observation of divalent and trivalent signals from the Eu 4f shell. The study serves as well to explore the limits of density functional theory and the choice of exchange correlation functionals to describe such a phenomenon as a valence transition.
We present results of hard X-ray angle-resolved photoemission spectroscopy and photoemission diffraction measurements performed on high-quality single crystals of the valence transition compound EuPd2Si2 for temperatures 25~K ≤ T ≤ 300~K. At low temperatures we observe a Eu 4f valence v=2.5, % occupation number n=6.5, which decreases to v=2.1 for temperatures above the valence transition around TV≈160~K. The experimental valence numbers resulting from an evaluation of the Eu(III)/Eu(II) 3d core levels, are used for calculating band structures using density functional theory. The valence transition significantly changes the band structure as determined by angle-resolved photoemission spectroscopy. In particular, the Eu 5d valence bands are shifted to lower binding energies with increasing Eu 4f occupancy. To a lesser extent, bands derived from the Si 3p and Pd 4d orbitals are also affected. This observation suggests a partial charge transfer between Eu and Pd/Si sites. Comparison with {\it ab-initio} theory shows a good agreement with experiment, in particular concerning the unequal band shift with increasing Eu 4f occupancy.
In magic angle twisted bilayer graphene, transport, thermodynamic and spectroscopic experiments pinpoint at a competition between distinct low-energy states with and without electronic order, as well as a competition between localized and delocalized charge carriers. In this study, we utilize Dynamical Mean Field Theory (DMFT) on the topological heavy Fermion (THF) model of twisted bilayer graphene to investigate the emergence of electronic correlations and long-range order in the absence of strain. We explain the nature of emergent insulating and correlated metallic states, as well as transitions between them driven by three central phenomena: (i) the formation of local spin and valley isospin moments around 100K, (ii) the ordering of the local isospin moments around 10K, and (iii) a cascadic redistribution of charge between localized and delocalized electronic states upon doping. At integer fillings, we find that low energy spectral weight is depleted in the symmetric phase, while we find insulating states with gaps enhanced by exchange coupling in the zero-strain ordered phases. Doping away from integer filling results in distinct metallic states: a "bad metal" above the ordering temperature, where coherence of the low-energy electronic excitations is suppressed by scattering off the disordered local moments, and a "good metal" in the ordered states with coherence of quasiparticles facilitated by isospin order. Upon doping, there is charge transfer between the localized and delocalized orbitals of the THF model such that they get periodically filled and emptied in between integer fillings. This charge reshuffling manifests itself in cascades of doping-induced Lifshitz transitions, local spectral weight redistributions and periodic variations of the electronic compressibility ranging from nearly incompressible to negative.
Strontium ruthenate Sr2RuO4 is an unconventional superconductor whose pairing symmetry has not been fully clarified, despite more than two decades of intensive research. Recent NMR Knight shift experiments have rekindled the Sr2RuO4 pairing debate by giving strong evidence against all odd-parity pairing states, including chiral p-wave pairing that was for a long time the leading pairing candidate. Here, we exclude additional pairing states by analyzing recent elastocaloric measurements [YS. Li et al., Nature 607, 276--280 (2022)]. To be able to explain the elastocaloric experiment, we find that unconventional even-parity pairings must include either large dx2−y2-wave or large {dxz∣dyz}-wave admixtures, where the latter possibility arises because of the body-centered point group symmetry. These {dxz∣dyz}-wave admixtures take the form of distinctively body-centered-periodic harmonics that have horizontal line nodes. Hence gxy(x2−y2)-wave and dxy-wave pairings are excluded as possible dominant even pairing states.
The existence of bound states induced by local impurities coupled to an insulating host depends decisively on the global topological properties of the host's electronic structure. In this context, we consider magnetic impurities modelled as classical unit-length spins that are exchange-coupled to the spinful Haldane model on the honeycomb lattice. We investigate the spectral flow of bound states with the coupling strength J in both the topologically trivial and Chern-insulating phases. In addition to conventional k-space topology, an additional, spatially local topological feature is available, based on the space of impurity-spin configurations forming, in case of R impurities, an R-fold direct product of two-dimensional spheres. Global k-space and local S-space topology are represented by different topological invariants, the first (k-space) Chern number and the R-th (S-space) spin-Chern number. We demonstrate that there is a local S-space topological transition as a function of J associated with a change in the spin Chern number and work out the implications of this for the J-dependent local electronic structure close to the impurities and, in particular, for in-gap bound states. The critical exchange couplings' dependence on the parameters of the Haldane model, and thus on the k-space topological state, is obtained numerically to construct local topological phase diagrams for systems with R=1 and R=2 impurity spins.
Although iron-based catalysts are regarded as a promising alternative to precious metal catalysts, their precise electronic structures during catalysis still pose challenges for computational descriptions. A particularly urgent question is the influence of the environment on the electronic structure, and how to describe this properly with computational methods. Here, we study an iron porphyrin chloride complex adsorbed on a graphene sheet using density functional theory calculations to detail how much the electronic structure is influenced by the presence of a graphene layer. Our results indicate that weak interactions due to van der Waals forces dominate between the porphyrin complex and graphene, and only a small amount of charge is transferred between the two entities. Furthermore, the interplay of the ligand field environment, strong p − d hybridization, and correlation effects within the complex are strongly involved in determining the spin state of the iron ion. By bridging molecular chemistry and solid state physics, this study provides first steps towards a joint analysis of the properties of iron-based catalysts from first principles.