arXiv subjects

Frank M. F. de Groot

Publications and source records attributed to Frank M. F. de Groot.

17 recordsLinked to original sources

arXiv2026

The Propagating Nature of Single- and Multimagnons in LaCrO$_3$

The dispersion of an excitation is commonly used to infer its microscopic character: dispersive modes are associated with propagation, whereas nondispersive features are often interpreted as localized. This distinction becomes less straightforward for composite excitations, whose spectral maxima can remain nearly dispersionless even when they are built from propagating quasiparticles. Here we use momentum- and temperature-dependent resonant inelastic X-ray scattering (RIXS) to reveal the origin of multimagnon excitations in antiferromagnetic LaCrO$_3$. Whereas the single magnon disperses strongly, the two- and three-magnon features remain nearly flat. On approaching the Neel temperature, thermal population of the magnon band produces an anti-Stokes branch and opens an additional three-magnon channel involving the creation of two magnons and annihilation of one. Its energy and momentum dependence are reproduced by a thermally weighted multimagnon joint density of states calculations. These results establish thermal population as a means of exposing the propagating constituents hidden within nondispersive composite excitations, and position RIXS as a probe of multimagnon dynamics and, ultimately, magnon-magnon interactions.

cond-mat.str-el↗

arXiv2026

Synthesis of epitaxial TaO$_2$ thin films on Al$_2$O$_3$ by suboxide molecular-beam epitaxy and thermal laser epitaxy

Tantalum dioxide (TaO2) is a metastable tantalum compound. Here, we report the epitaxial stabilization of TaO2 on Al2O3 (1-102) (r-plane sapphire) substrates using suboxide molecular-beam epitaxy (MBE) and thermal laser epitaxy (TLE), demonstrating single-oriented, monodomain growth of anisotropically strained thin films. Microstructural investigation is performed using synchrotron X-ray diffraction and scanning transmission electron microscopy. The tetravalent oxidation state of tantalum is confirmed using X-ray absorption and photoemission spectroscopy as well as electron energy-loss spectroscopy. Optical properties are investigated via spectroscopic ellipsometry and reveal a 0.3 eV Mott gap of the tantalum 5d electrons. Density-functional theory and group theoretical arguments are used to evaluate the limited stability of the rutile phase and reveal the potential to unlock a hidden metal-insulator transition concomitant with a structural phase transition to a distorted rutile phase, akin to NbO2. Our work expands the understanding of tantalum oxides and paves the way for their integration into next-generation electronic and photonic devices.

cond-mat.mtrl-sci↗

arXiv2025

Interfacial Control of Orbital Occupancy and Spin State in LaCoO$_3$

Transition metal oxides exhibit a wide range of tunable electronic properties arising from the complex interplay of charge, spin, and lattice degrees of freedom, governed by their $d$ orbital configurations, making them particularly interesting for oxide electronics and (electro)catalysis. Perovskite oxide heterointerfaces offer a promising route to engineer these orbital states. In this work, we tune the Co $3d$ orbital occupancy in LaCoO$_3$ from a partial $d^7$ to a partial $d^5$ state through interfacial engineering with LaTiO$_3$, LaMnO$_3$, LaAlO$_3$ and LaNiO$_3$. Using X-ray absorption spectroscopy combined with charge transfer multiplet calculations, we identify differences in the Co valence and spin state for the series of oxide heterostructures. LaTiO$_3$ and LaMnO$_3$ interfaces result in interfacial charge transfer towards LaCoO$_3$, resulting in a partial $d^7$ orbital occupancy, while a LaNiO$_3$ interface results in a partial Co $d^5$ occupancy. Strikingly, a LaAlO$_3$ spacer layer between LaNiO$_3$ and LaCoO$_3$ results in a Co $d^6$ low spin state. These results indicate that the Co spin state, like the valence state, is governed by the interfacial environment. High-resolution scanning transmission electron microscopy imaging reveals a clear connection between strain and spin configuration, emphasizing the importance of structural control at oxide interfaces. Overall, this work demonstrates that interfacial engineering simultaneously governs orbital occupancy and spin state in correlated oxides, advancing spin-engineering strategies in correlated oxides and offering new insights for the rational design of functional oxide heterostructures.

cond-mat.mtrl-sci↗

arXiv2025

Redox Chemistry of LiCoO$_2$, LiNiO$_2$, and LiNi$_{1/3}$Mn$_{1/3}$Co$_{1/3}$O$_2$ Cathodes: Deduced via XPS, DFT+DMFT, and Charge Transfer Multiplet Simulations

Understanding the evolution of the physicochemical bulk properties during the Li deintercalation (charging) process is critical for optimizing battery cathode materials. In this study, we combine X-ray photoelectron spectroscopy (XPS), density functional theory plus dynamical mean-field theory (DFT+DMFT) calculations, and charge transfer multiplet (CTM) model simulations to investigate how hybridization between transition metal (TM) 3d and oxygen 2p orbitals evolves with Li deintercalation. Based on the presented approach combining theoretical calculations and experimental studies of pristine and deintercalated cathodes, two important problems of ion batteries can be addressed: i) the detailed electronic structure and involved changes with deintercalation providing information of the charge compensation mechanism, and ii) the precise experimental analysis of XPS data which are dominated by charge transfer coupled to final-state effects affecting the satellite structure. As main result for the investigated Li TM oxides, it can be concluded that the electron transfer coupled to the Li$^{+}$-ion migration does not follow a rigid band model but is modified due to changes in TM 3d and O 2p states hybridization. Furthermore, this integrated approach identifies the 2p XPS satellite peak intensity of TM as an effective indicator of the redox chemistry. With that the redox chemistry of cathodes can be deduced, thus offering a foundation for designing more efficient battery materials.

cond-mat.mtrl-sci↗

arXiv2024

Spin-orbital excitations encoding the magnetic phase transition in the van der Waals antiferromagnet FePS$_{3}$

In the rich phases of van der Waals (vdW) materials featuring intertwined electronic order and collective phenomena, characterizing elementary dynamics that entail the low-energy Hamiltonian and electronic degrees of freedom is of paramount importance. Here we performed resonant inelastic X-ray scattering (RIXS) to elaborate the spin-orbital ground and excited states of the vdW antiferromagnetic insulator FePS$_{3}$, as well as their relation to magnetism. We observed the spectral enhancement of spin-orbital multiplet transitions about $\sim$ 100 and $\sim$ 220 meV, as well as quasielastic response, when entering the zig-zag antiferromagnetic phase, where the spectral changes develop an order-parameter-like evolution with temperature. By comparing with ligand field theory calculations, we discovered the essential role of trigonal lattice distortion and negative metal-ligand charge-transfer to account for these emergent excitations. Such spectral profiles are further examined upon confinement by mechanical exfoliation. We reveal their spectral robustness down to the few atomic layer limit, in accordance with the persistent antiferromagnetic state previously reported in optical measurements. Our study demonstrates the versatile RIXS capability that resolves magneto-crystalline anisotropy and charge-transfer energetics. These provide the crucial insight to understand how the spontaneous magnetic symmetry-breaking stabilizes in the quasi-two-dimensional limit for the vdW magnet FePS$_{3}$.

cond-mat.str-el↗

arXiv2024

Atomic multiplet and charge-transfer screening effects in 1$s$ and 2$p$ core-level X-ray photoelectron spectra of early 3$d$ transition-metal oxides

We present a comparative analysis of 1$s$ and 2$p$ core-level hard X-ray photoelectron spectroscopy (HAXPES) spectra in metallic VO$_2$ and CrO$_2$. Even though the V 1$s$ and 2$p$ spectra in VO$_2$ display similar line shapes except the absence or presence of a spin-orbit coupling splitting, the Cr 1$s$ and 2$p$ spectra exhibit distinct main-line shapes. The experimental HAXPES spectra are analyzed by the Anderson impurity model based on the density functional theory + dynamical mean-field theory and a conventional MO$_6$ cluster model. We elucidate the complex interplay between formation of the intra-atomic multiplet and charge transfer effect on the chemical bonding followed by the 1$s$ and 2$p$ core electron excitations. We demonstrate the advantage of the 1$s$ excitations to the routinely-employed 2$p$ excitations for distinguishing between metal-ligand and metal-metal charge transfer contributions in early 3$d$ transition-metal oxides.

cond-mat.mtrl-sci↗

arXiv2024

Nature of excitons and their ligand-mediated delocalization in nickel dihalide charge-transfer insulators

The fundamental optical excitations of correlated transition-metal compounds are typically identified with multielectronic transitions localized at the transition-metal site, such as $dd$ transitions. In this vein, intense interest has surrounded the appearance of sharp, below band-gap optical transitions, i.e. excitons, within the magnetic phase of correlated Ni$^{2+}$ van der Waals magnets. The interplay of magnetic and charge-transfer insulating ground states in Ni$^{2+}$ systems raises intriguing questions on the roles of long-range magnetic order and of metal-ligand charge transfer in the exciton nature, which inspired microscopic descriptions beyond typical $dd$ excitations. Here we study the impact of charge-transfer and magnetic order on the excitation spectrum of the nickel dihalides (NiX$_2$, X $=$ Cl, Br, and I) using Ni-$L_3$ resonant inelastic x-ray scattering (RIXS). In all compounds, we detect sharp excitations, analogous to the recently reported excitons, and assign them to spin-singlet multiplets of octahedrally-coordinated Ni$^{2+}$ stabilized by intra-atomic Hund's exchange. Additionally, we demonstrate that these excitons are dispersive using momentum resolved RIXS. Our data evidence a ligand-mediated multiplet dispersion, which is tuned by the charge-transfer gap and independent of the presence of long-range magnetic order. This reveals the mechanisms governing non-local interactions of on-site $dd$ excitations with the surrounding crystal/magnetic structure, in analogy to ground state superexchange. These measurements thus establish the roles of magnetic order, self-doped ligand holes, and intersite coupling mechanisms for the properties of $dd$ excitations in charge-transfer insulators.

cond-mat.str-el↗

arXiv2023

Satellites in the Ti~1$s$ core level spectra of SrTiO$_3$ and TiO$_2$

Satellites in core level spectra of photoelectron spectroscopy (PES) can provide crucial information on the electronic structure and chemical bonding in materials, particular in transition metal oxides. This paper explores satellites of the Ti 1$s$ and 2$p$ core level spectra of SrTiO$_3$ and TiO$_2$. Conventionally, soft x-ray PES (SXPS) probes the Ti 2$p$ core level; however, it is not ideal to fully capture satellite features due to its inherent spin-orbit-splitting (SOS). Here, hard x-ray PES(HAXPES) provides access to the Ti 1$s$ spectrum instead, which allows us to study intrinsic charge responses upon core-hole creation without the complication from SOS and with favorable intrinsic linewidths. The experimental spectra are theoretically analyzed by two impurity models, including an Anderson impurity model (AIM) built on local density approximation (LDA) and dynamical mean-field theory (DMFT), and a conventional TiO$_6$ cluster model. The theoretical results emphasize the importance of explicit inclusion of higher-order Ti-O charge-transfer processes beyond the nearest-neighboring Ti-O bond to simulate the core level spectra of SrTiO$_3$ and TiO$_2$. The AIM approach with continuous bath orbitals provided by LDA+DMFT represents the experimental spectra well. Crucially, with the aid of the LDA+DMFT method, this paper provides a robust prescription of how to use the computationally cheap cluster model in fitting analyses of core level spectra.

cond-mat.mtrl-sci↗

arXiv2022

Electronic Excitations of Hematite Heteroepitaxial Films Measured by Resonant Inelastic X-Ray Scattering at the Fe L-edge

Resonant Inelastic X-Ray Scattering (RIXS) spectra of hematite were measured at the Fe L3-edge for heteroepitaxial thin films which were undoped and doped with 1% Ti, Sn or Zn, in the energy loss range in excess of 1 eV to study electronic transitions. The spectra were measured for several momentum transfers (q), conducted at both low temperature (T=14K) and room temperature. While we can not rule out dispersive features possibly owing to propagating excitations, the coarse envelopes of the general spectra did not appreciably change shape with q, implying that the bulk of the observed L-edge RIXS intensity originates from (mostly) non-dispersive ligand field (LF) excitations. Summing the RIXS spectra over q and comparing the results at T=14 K to those at T=300 K, revealed pronounced temperature effects, including an intensity change and energy shift of the 1.4 eV peak, a broadband intensity increase of the 3-4 eV range, and higher energy features. The q-summed spectra and their temperature dependences are virtually identical for nearly all of the samples with different dopants, save for the temperature dependence of the Ti-doped sample's spectrum, which we attribute to being affected by a large number of free charge carriers. Comparing with magnetization measurements for different temperatures and dopings likewise did not show a clear correlation between the RIXS spectra and the magnetic ordering states. To clarify the excited states, we performed spin multiplet calculations which were in excellent agreement with the RIXS spectra over a wide energy range and provide detailed electronic descriptions of the excited states. The implications of these findings to the photoconversion efficiency of hematite photoanodes is discussed.

cond-mat.str-el↗

arXiv2021

Complete crystallographic, spin-electronic and magnetic structure of (Co0.2Cr0.2Fe0.2Mn0.2Ni0.2)3O4: Unraveling the suppression of entropy in high entropy oxides

High entropy oxides (HEOs) are a rapidly emerging class of functional materials consisting of multiple principal cations. The original paradigm of HEOs assumes cationic occupations with the highest possible configurational entropy allowed by the composition and crystallographic structure. However, the fundamental question remains on the actual degree of configurational disorder in HEOs, especially, in systems with a low enthalpy barriers for cation anti-site mixing. Considering the experimental limitations due to the presence of multiple principal cations in HEOs, here we utilize a robust and cross-referenced characterization approach using soft X-ray magnetic circular dichroism, hard X-ray absorption spectroscopy, Mössbauer spectroscopy, neutron powder diffraction and SQUID magnetometry to study the competition between crystal field stabilization energy and configurational entropy governing the cation occupation in a spinel HEO (S-HEO), (Co$_{0.2}$Cr$_{0.2}$Fe$_{0.2}$Mn$_{0.2}$Ni$_{0.2}$)$_3$O$_4$. In contrast to the previous studies, the derived complete structural and spin-electronic model, (Co$_{0.6}$Fe$_{0.4}$)(Cr$_{0.3}$Fe$_{0.1}$Mn$_{0.3}$Ni$_{0.3}$)$_2$O$_4$, highlights a significant deviation from the hitherto assumed paradigm of entropy-driven non-preferential distribution of cations in HEOs. An immediate correlation of this result can be drawn with bulk as well as the local element specific magnetic properties, which are intrinsically dictated by cationic occupations in spinels. The real local lattice picture presented here provides an alternate viewpoint on ionic arrangement in HEOs, which is of fundamental interest for predicting and designing their structure-dependent functionalities.

cond-mat.mtrl-sci↗

arXiv2021

Damping of spinful excitons in LaCoO$_3$ by thermal fluctuations: Theory and experiment

We present Co $L_3$-edge resonant inelastic x-ray scattering (RIXS) of bulk LaCoO$_3$ across the thermally-induced spin-state crossover around 100~K. Owing to a high energy resolution of 25~meV, we observe unambiguously the dispersion of the intermediate-spin (IS) excitations in the low temperature regime. Approaching the intermediate temperature regime, the IS excitations are damped and the bandwidth is reduced. The observed behavior can be well described by a model of mobile IS excitons with strong attractive interaction, which we solve using dynamical mean-field theory for hard-core bosons. Our results provide a detailed mechanism of how high-spin (HS) and IS excitations interact to establish the physical properties of cobaltite perovskites.

cond-mat.str-el↗

arXiv2020

Revealing the site selective local electronic structure of Co$_{3}$O$_{4}$ using $2p3d$ resonant inelastic X-ray scattering

We investigate mixed-valence oxide Co$_3$O$_4$ using Co $2p3d$ resonant inelastic X-ray scattering (RIXS). By setting resonant edges at Co$^{2+}$ and Co$^{3+}$ ions, the $dd$ excitations on the two Co sites are probed selectively, providing detailed information on the local electronic structure of Co$_3$O$_4$. The $2p3d$ RIXS result reveals the $^4$T$_{2}$ excited state of tetrahedral Co$^{2+}$ site at 0.5 eV beyond the discriminative power of optical absorption spectroscopies. Additionally, the $^3$T$_{2g}$ excited stated at 1.3 eV is uniquely identified for the octahedral Co$^{3+}$ site. Guided by cluster multiplet simulations, the ground-state character of the Co$^{2+}$ and Co$^{3+}$ site is determined to be high-spin $^4$A$_{2}$(T$_d$) and low-spin $^1$A$_{1g}$(O$_h$), respectively. This indicates that only the Co$^{2+}$ site is magnetically active site at low-temperatures in Co$_3$O$_4$. The ligand-to-metal charge transfer analysis suggests a formation of a strong covalent bonding between Co and O ions at the Co$^{3+}$ site, while Co$^{2+}$ is rather ionic.

cond-mat.mtrl-sci↗

arXiv2019

Charge-transfer effect in hard x-ray 1$s$ and 2$p$ photoemission spectra: LDA+DMFT and cluster-model analysis

We study $1s$ and $2p$ hard x-ray photoemission spectra (XPS) in a series of late transition metal oxides: Fe$_2$O$_3$ (3$d^{5}$), FeTiO$_3$ (3$d^{6}$), CoO (3$d^{7}$) and NiO (3$d^{8}$). The experimental spectra are analyzed with two theoretical approaches: the MO$_6$ cluster model and the local density approximation (LDA) + dynamical mean-field theory (DMFT). Owing to the absence of the core-valence multiplets and spin-orbit coupling, 1$s$ XPS is found to be a sensitive probe of chemical bonding and nonlocal charge-transfer screening, providing complementary information to 2$p$ XPS. The 1$s$ XPS spectra are used to assess the accuracy of the $ab$-initio LDA+DMFT approach, developed recently to study the material-specific charge-transfer effects in core-level XPS.

cond-mat.mtrl-sci↗

arXiv2018

Excitonic dispersion of the intermediate-spin state in LaCoO$_3$ revealed by resonant inelastic X-ray scattering

More than 50 years ago the electron-hole attraction was proposed to drive narrow gap semiconductors or semimetals to a new phase, the excitonic insulator. The experimental proof of its existence in bulk materials remains elusive. In strongly correlated insulators, the proximity of the excitonic insulator phase is reflected by the presence of dispersive electron-hole excitations with a small gap above a singlet ground state. Recently, such an excitation spectrum was proposed to be realized in perovskite oxide LaCoO$_3$. In this Letter we use Co $L_3$-edge resonant inelastic X-ray scattering to put this proposal to experimental test.

cond-mat.str-el↗

arXiv2017

Electronic structure of Pr2MnNiO6 from x-ray photoemission, absorption and density functional theory

The electronic structure of double perovskite Pr2MnNiO6 is studied using core x-ray photoelectron spectroscopy and x-ray absorption spectroscopy. The 2p x-ray absorption spectra show that Mn and Ni are in 2+ and 4+ states respectively. Using charge transfer multiplet analysis of Ni and Mn 2p XPS spectra, we find charge transfer energies Δ of 3.5 and 2.5 eV for Ni and Mn respectively. The ground state of Ni2+ and Mn4+ reveal a higher d electron count of 8.21 and 3.38 respectively as compared to the atomic values of 8.00 and 3.00 respectively thereby indicating the covalent nature of the system. The O 1s edge absorption spectra reveal a band gap of 0.9 eV which is comparable to the value obtained from first principle calculations for U-J >= 2 eV. The density of states clearly reveal a strong p-d type charge transfer character of the system, with band gap proportional to average charge transfer energy of Ni2+ and Mn4+ ions.

cond-mat.str-el↗

arXiv2017

Magnetic states at the surface of alpha-Fe2O3 thin films doped with Ti, Zn or Sn

The spin states at the surface of epitaxial thin films of hematite, both undoped and doped with 1% Ti, Sn or Zn, respectively, were probed with x-ray magnetic linear dichroism (XMLD) spectroscopy. Morin transitions were observed for the undoped (T_M~200 K) and Sn-doped (T_M~300 K) cases, while Zn and Ti-doped samples were always in the high and low temperature phases, respectively. In contrast to what has been reported for bulk hematite doped with the tetravalent ions Sn4+ and Ti4+, for which T_M dramatically decreases, these dopants substantially increase T_M in thin films, far exceeding the bulk values. The normalized Fe LII-edge dichroism for T T_M state was achieved. The temperature dependence of the critical field for the Sn-doped sample was characterized in detail. It was demonstrated the sample-to-sample variations of the Fe LIII-edge spectra were, for the most part, determined solely by the spin orientation state. Calculations of the polarization-depedent spectra based on a spin-multiplet model were in reasonable agreement with the experiment and showed a mixed excitation character of the peak structures.

cond-mat.mtrl-sci↗

arXiv2008

Intersite 4p-3d hybridization in cobalt oxides: a resonant x-ray emission spectroscopy study

We report on strong dipole transitions to 3d orbitals of neighboring Co atoms in the Co 1s x-ray absorption pre-edge. They are revealed by applying high-resolution resonant x-ray emission spectroscopy (RXES) to compounds containing CoO6 clusters. When contrasted to quadrupole local 1s3d excitations, these non-local 1s3d transitions are identified by their energy dispersion and angular dependence, their sensitivity to second-shell effects (i.e. the connection mode of the CoO6 octahedra and the bond lengths), and an upwards energy shift of 2.5 eV due to the poorer screening of the core hole. The experiment reveals that the intensity of the non-local transitions gauges the oxygen-mediated 4p-O-3d intersite hybridization. We propose a revised interpretation of the pre-edges of transition metal compounds. Detailed analysis of these new features in the pre-edge offers a unique insight in the oxygen mediated metal-metal interactions in transition metal-based systems, which is a crucial aspect in orbital ordering and related electronic and magnetic properties. In addition, the exceptional resolving power of the present 1s2p RXES experiment allows us to demonstrate the coherent second-order nature of the underlying scattering process.

cond-mat.str-el↗