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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.
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 origin is not yet completely understood. Here, we investigate the mechanism of the valence transition under volume compression by density functional theory calculations (DFT). Our analysis suggests that the transition is a consequence of an enhanced c−f hybridization between localized Eu 4f states and itinerant conduction states (Eu 5d, Pd 4d, and Si 3p) where the interplay of the electronic bandwidth, crystal field environment, Coulomb repulsion, Hund's coupling and spin-orbit coupling plays a crucial role for the transition to happen. The change in the electronic structure is intimately related to the volume reduction where Eu-Pd(Si) bond lengths shorten. In a next step we compare 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.
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.
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.