arXiv subjects

P. H. M. van Loosdrecht

Publications and source records attributed to P. H. M. van Loosdrecht.

At least 19 recordsLinked to original sources

arXiv2026

Between Mott and cluster Mott: spin-orbit entangled dimer singlets in Ba$_3$CeRu$_2$O$_9$

The hexagonal 4d ruthenates Ba3MRu2O9 host structural dimers and exhibit a delicate balance of competing interactions. Hund's coupling, trigonal crystal-field splitting, and hopping for $a_{1g}$ and $e_g^π$ orbitals all fall within a narrow energy window. This yields a series of possible ground states, ranging from the localized Mott limit with (anti-) ferromagnetic exchange coupling via orbital-selective behavior to the cluster Mott limit with quasimolecular orbitals that are delocalized over the two dimer sites. Using resonant inelastic x-ray scattering, we show that Ba3CeRu2O9 with four holes per dimer resides in the intricate crossover regime between the localized Mott case and the quasimolecular limit. The spin-orbit entangled singlet ground state predominantly shows a Mott-like charge distribution with two holes per Ru site. At the same time, spin and orbital occupation contradict an exchange-based Mott scenario but agree with a cluster Mott approach. A quasimolecular trial wave function describes more than 70% of the ground state. In this crossover regime, small changes of, e.g., the crystal field may strongly affect the character of electronic states.

cond-mat.str-el↗

arXiv2024

Quasimolecular electronic structure of the trimer iridate Ba$_4$NbIr$_3$O$_{12}$

The insulating mixed-valent Ir$^{+3.66}$ compound Ba$_4$NbIr$_3$O$_{12}$ hosts two holes per Ir$_3$O$_{12}$ trimer unit. We address the electronic structure via resonant inelastic x-ray scattering (RIXS) at the Ir $L_3$ edge and exact diagonalization. The holes occupy quasimolecular orbitals that are delocalized over a trimer. This gives rise to a rich intra-$t_{2g}$ excitation spectrum that extends from 0.5 eV to energies larger than 2 eV. Furthermore, it yields a strong modulation of the RIXS intensity as a function of the transferred momentum q. A clear fingerprint of the quasimolecular trimer character is the observation of two modulation periods, $2π/d$ and $2π/2d$, where d and 2d denote the intratrimer Ir-Ir distances. We discuss how the specific modulation reflects the character of the wavefunction of an excited state. Our quantitative analysis shows that spin-orbit coupling $λ$ of about 0.4 eV is decisive for the character of the electronic states, despite a large hopping $t_{a_{1g}}$ of about 0.8 eV. The ground state of a single trimer is described very well by both holes occupying the bonding j=1/2 orbital, forming a vanishing quasimolecular moment with J=0.

cond-mat.str-el↗

arXiv2024

Spin-orbital-lattice entanglement in the ideal j=1/2 compound K$_2$IrCl$_6$

Mott insulators with spin-orbit entangled j=1/2 moments host intriguing magnetic properties. The j=1/2 wave function requires cubic symmetry, while a noncubic crystal field mixes j=1/2 and 3/2 character. Spectroscopic studies of $5d^5$ iridates typically claim noncubic symmetry, e.g., based on a splitting of the excited j=3/2 quartet. A sizable splitting is particularly puzzling in antifluorite-type K$_2$IrCl$_6$, a frustrated fcc quantum magnet with global cubic symmetry. It raises the fundamental question about the stability of j=1/2 moments against magneto-elastic coupling. Combining resonant inelastic x-ray scattering with optical spectroscopy, we demonstrate that the multi-peak line shape in K$_2$IrCl$_6$ reflects a vibronic character of the j=3/2 states rather than a noncubic crystal field. The quasimolecular crystal structure with well separated IrCl$_6$ octahedra explains the existence of well-defined sidebands that are usually smeared out in solids. Our results highlight the spin-orbital-lattice entangled character of cubic K$_2$IrCl$_6$ with ideal j=1/2 moments.

cond-mat.str-el↗

arXiv2023

Spin-orbit coupling in a half-filled $t_{2g}$ shell: the case of $5d^3$ K$_2$ReCl$_6$

The half-filled $t_{2g}$ shell of the $t_{2g}^3$ configuration usually, in LS coupling, hosts a S = 3/2 ground state with quenched orbital moment. This state is not Jahn-Teller active. Sufficiently large spin-orbit coupling $ζ$ has been predicted to change this picture by mixing in orbital moment, giving rise to a sizable Jahn-Teller distortion. In $5d^3$ K$_2$ReCl$_6$ we study the electronic excitations using resonant inelastic x-ray scattering (RIXS) and optical spectroscopy. We observe on-site intra-$t_{2g}$ excitations below 2 eV and corresponding overtones with two intra-$t_{2g}$ excitations on adjacent sites, the Mott gap at 2.7 eV, $t_{2g}$-to-$e_g$ excitations above 3 eV, and charge-transfer excitations at still higher energy. The intra-$t_{2g}$ excitation energies are a sensitive measure of $ζ$ and Hund's coupling $J_H$. The sizable value of $ζ\approx$ 0.29 eV places K$_2$ReCl$_6$ into the intermediate coupling regime, but $ζ/J_H \approx 0.6$ is not sufficiently large to drive a pronounced Jahn-Teller effect. We discuss the ground state wavefunction in a Kanamori picture and find that the S = 3/2 multiplet still carries about 97 % of the weight. However, the finite admixture of orbital moment allows for subtle effects. We discuss small temperature-induced changes of the optical data and find evidence for a lowering of the ground state by about 3 meV below the structural phase transitions.

cond-mat.str-el↗

arXiv2023

Strong terahertz third-harmonic generation by kinetic heavy quasiparticles in CaRuO$_3$

We report on time-resolved nonlinear terahertz spectroscopy of a strongly correlated ruthenate, CaRuO$_3$, as a function of temperature, frequency and terahertz field strength. Third-harmonic radiation for frequencies up to 2.1 THz is observed evidently at low temperatures below 80 K, where the low-frequency linear dynamical response deviates from the Drude model and a coherent heavy quasiparticle band emerges by strong correlations associated with the Hund's coupling.Phenomenologically, by taking an experimentally observed frequency-dependent scattering rate, the deviation of the field driven kinetics from the Drude behavior is reconciled in a time-dependent Boltzmann description, which allows an attribution of the observed third-harmonic generation to the terahertz field driven nonlinear kinetics of the heavy quasiparticles.

cond-mat.str-el↗

arXiv2023

Quasimolecular $J_{\rm tet}$=3/2 moments in the cluster Mott insulator GaTa$_4$Se$_8$

Quasimolecular orbitals in cluster Mott insulators provide a route to tailor exchange interactions, which may yield novel quantum phases of matter. We demonstrate the cluster Mott character of the lacunar spinel GaTa$_4$Se$_8$ using resonant inelastic x-ray scattering (RIXS) at the Ta $L_3$ edge. Electrons are fully delocalized over Ta$_4$ tetrahedra, forming quasimolecular $J_{\rm tet}$=3/2 moments. The modulation of the RIXS intensity as function of the transferred momentum q allows us to determine the cluster wavefunction, which depends on competing intracluster hopping terms that mix states with different character. This mixed wavefunction is decisive for the macroscopic properties since it affects intercluster hopping and exchange interactions and furthermore renormalizes the effective spin-orbit coupling constant. The versatile wavefunction, tunable via intracluster hopping, opens a new perspective on the large family of lacunar spinels and cluster Mott insulators in general.

cond-mat.str-el↗

arXiv2023

Electronic excitations in $5d^4$ J=0 Os$^{4+}$ halides studied by RIXS and optical spectroscopy

We demonstrate that the cubic antifluorite-type halides K$_2$OsCl$_6$, K$_2$OsBr$_6$, and Rb$_2$OsBr$_6$ are excellent realizations of non-magnetic J=0 compounds. The magnetic susceptibility shows the corresponding Van-Vleck type behavior and no sign of defects. We investigate the electronic excitations with two complementary techniques, resonant inelastic x-ray scattering (RIXS) and optical spectroscopy. This powerful combination allows us to thoroughly study, e.g., on-site intra-$t_{2g}$ excitations and $t_{2g}$-to-$e_g$ excitations as well as inter-site excitations across the Mott gap and an exciton below the gap. In this way, we determine the electronic parameters with high accuracy, altogether yielding a comprehensive picture. In K$_2$OsCl$_6$, we find the spin-orbit coupling constant $ζ$=0.34 eV, Hund's coupling $J_H$=0.43 eV, the onset of excitations across the Mott gap at $Δ$=2.2 eV, the cubic crystal-field splitting 10Dq=3.3 eV, and the charge-transfer energy $Δ_{CT}$=4.6 eV. With $J_H/ζ$=1.3, K$_2$OsCl$_6$ is in the intermediate-coupling regime. In a $t_{2g}$-only Kanamori picture, the above values correspond to $ζ^{eff}$=0.41 eV and $J_H^{eff}$=0.28 eV, which is very close to results reported for related $5d^4$ iridates. In the tetragonal phase at 5 K, the non-cubic crystal field causes a peak splitting of the J=1 state as small as 4 meV. Compared to K$_2$OsCl$_6$, the bromides K$_2$OsBr$_6$ and Rb$_2$OsBr$_6$ show about 12-14 % smaller values of 10Dq and $Δ_{CT}$, while the spin-orbit-entangled intra-$t_{2g}$ excitations below 2 eV and hence $ζ$ and $J_H$ are reduced by less than 4 %. Furthermore, the Mott gap in K$_2$OsBr$_6$ is reduced to about 1.8 eV.

cond-mat.str-el↗

arXiv2023

Local symmetry breaking and low-energy continuum in K$_2$ReCl$_6 $

Using polarization selective spontaneous Raman scattering, we have investigated the 5$d$ transition metal compound K$_2$ReCl$_6$ which displays a series of structural phase transitions. We observe a violation of the Raman selection rules in the cubic high temperature phase as well as a low-energy scattering continuum persistent throughout the investigated temperature range from 300 down to 5 K. The continuum couples to one of the phonon modes at temperatures above the lowest structural phase transition at 76 K. We propose a common origin of these observations caused by local fluctuations in the orientation of the ReCl$_6$ octahedra which locally break the long-range cubic symmetry. Consistent results from the related non-magnetic compound K$_2$SnCl$_6$ support this interpretation.

cond-mat.str-el↗

arXiv2023

RIXS observation of bond-directional nearest-neighbor excitations in the Kitaev material Na$_2$IrO$_3$

Spin-orbit coupling locks spin direction and spatial orientation and generates, in semi-classical magnets, a local spin easy-axis and associated ordering. Quantum spin-1/2's defy this fate: rather than spins becoming locally anisotropic, the spin-spin interactions do. Consequently interactions become dependent on the spatial orientation of bonds between spins, prime theoretical examples of which are Kitaev magnets. Bond-directional interactions imply the existence of bond-directional magnetic modes, predicted spin excitations that render crystallographically equivalent bonds magnetically inequivalent, which yet have remained elusive experimentally. Here we show that resonant inelastic x-ray scattering allows us to explicitly probe the bond-directional character of magnetic excitations. To do so, we use a scattering plane spanned by one bond and the corresponding spin component and scan a range of momentum transfer that encompasses multiple Brillouin zones. Applying this approach to Na$_2$IrO$_3$ we establish the different bond-directional characters of magnetic excitations at 10 meV and 45 meV. Combined with the observation of spin-spin correlations that are confined to a single bond, this experimentally validates the Kitaev character of exchange interactions long proposed for this material.

cond-mat.str-el↗

arXiv2022

High-order nonlinear terahertz probing of the two-band superconductor MgB$_2$: Third- and fifth-order harmonic generation

We report on high-order harmonic generation in the two-band superconductor MgB$_2$ driven by intense terahertz electromagnetic pulses. Third- and fifth-order harmonics are resolved in time domain and investigated as a function of temperature and in applied magnetic fields crossing the superconducting phase boundary. The high-order harmonics in the superconducting phase reflects nonequilibrium dynamics of the superconducting order parameter in MgB$_2$, which is probed via nonlinear coupling to the terahertz field. The observed temperature and field dependence of the nonlinear response allows to establish the superconducting phase diagram.

cond-mat.supr-con↗

arXiv2022

Quasimolecular electronic structure of the spin-liquid candidate Ba$_3$InIr$_2$O$_9$

The mixed-valent iridate Ba3InIr2O9 has been discussed as a promising candidate for quantum spin-liquid behavior. The compound exhibits Ir$^{4.5+}$ ions in face-sharing IrO6 octahedra forming Ir2O9 dimers with three t2g holes per dimer. Our results establish Ba3InIr2O9 as a cluster Mott insulator. Strong intra-dimer hopping delocalizes the three t2g holes in quasi-molecular dimer states while inter-dimer charge fluctuations are suppressed by Coulomb repulsion. The magnetism of Ba3InIr2O9 emerges from spin-orbit entangled quasi-molecular moments with yet unexplored interactions, opening up a new route to unconventional magnetic properties of 5d compounds. Using single-crystal x-ray diffraction we find the monoclinic space group C2/c already at room temperature. Dielectric spectroscopy shows insulating behavior. Resonant inelastic x-ray scattering (RIXS) reveals a rich excitation spectrum below 1.5 eV with a sinusoidal dynamical structure factor that unambiguously demonstrates the quasi-molecular character of the electronic states. Below 0.3 eV, we observe a series of excitations. According to exact diagonalization calculations, such low-energy excitations reflect the proximity of Ba3InIr2O9 to a hopping-induced phase transition based on the condensation of a quasi-molecular spin-orbit exciton. The dimer ground state roughly hosts two holes in a bonding j=1/2 orbital and the third hole in a bonding j=3/2 orbital.

cond-mat.str-el↗

arXiv2022

RIXS interferometry and the role of disorder in the quantum magnet Ba$_3$Ti$_{3-x}$Ir$_{x}$O$_9$

Motivated by several claims of spin-orbit driven spin-liquid physics in hexagonal Ba$_3$Ti$_{3-x}$Ir$_x$O$_9$ hosting Ir2O9 dimers, we report on resonant inelastic x-ray scattering (RIXS) at the Ir L3 edge for different x. We demonstrate that magnetism in Ba$_3$Ti$_{3-x}$Ir$_x$O$_9$ is governed by an unconventional realization of strong disorder, where cation disorder affects the character of the local moments. RIXS interferometry, studying the RIXS intensity over a broad range of transferred momentum q, is ideally suited to assign different excitations to different Ir sites. We find pronounced Ir-Ti site mixing. Both ions are distributed over two crystallographically inequivalent sites, giving rise to a coexistence of quasimolecular singlet states on Ir2O9 dimers and spin-orbit entangled j=1/2 moments of 5d$^5$ Ir$^{4+}$ ions. RIXS reveals different kinds of strong magnetic couplings for different bonding geometries, highlighting the role of cation disorder for the suppression of long-range magnetic order in this family of compounds.

cond-mat.str-el↗

arXiv2020

Nonequilibrium quasistationary spin disordered state in the Kitaev-Heisenberg magnet $α$-RuCl$_3$

Excitation by light pulses enables the manipulation of phases of quantum condensed matter. Here, we photoexcite high-energy holon-doublon pairs as a way to alter the magnetic free energy landscape of the Kitaev-Heisenberg magnet $α$-RuCl$_3$, with the aim to dynamically stabilize a proximate spin liquid phase. The holon-doublon pair recombination through multimagnon emission is tracked through the time-evolution of the magnetic linear dichroism originating from the competing zigzag spin ordered ground state. A small holon-doublon density suffices to reach a spin disordered state. The phase transition is described within a dynamic Ginzburg-Landau framework, corroborating the quasistationary nature of the transient spin disordered phase. Our work provides insight into the coupling between the electronic and magnetic degrees of freedom in $α$-RuCl$_3$ and suggests a new route to reach a proximate spin liquid phase in Kitaev-Heisenberg magnets.

cond-mat.str-el↗

arXiv2019

Multiple Spin-Orbit Excitons and the Electronic Structure of $α$-RuCl$_3$

The honeycomb compound $α$-RuCl$_3$ is widely discussed as a proximate Kitaev spin-liquid material. This scenario builds on spin-orbit entangled $j = 1/2$ moments arising for a $t_{2g}^5$ electron configuration with strong spin-orbit coupling $λ$ and a large cubic crystal field. The low-energy electronic structure of $α$-RuCl$_3$, however, is still puzzling. In particular infrared absorption features at 0.30 eV, 0.53 eV, and 0.75 eV seem to be at odds with theory. Also the energy of the spin-orbit exciton, the excitation from $j = 1/2$ to 3/2, and thus the value of $λ$ are controversial. Combining infrared and Raman data, we show that the infrared features can be attributed to single, double, and triple spin-orbit excitons. We find $λ$ = 0.16 eV and $Δ$ =42(4) meV for the observed non-cubic crystal-field splitting, supporting the validity of the $j= 1/2$ picture for $α$-RuCl$_3$. The unusual strength of the double excitation is related to the underlying hopping interactions which form the basis for dominant Kitaev exchange.

cond-mat.str-el↗

arXiv2019

Dynamics of incoherent exciton formation in Cu$_2$O: Time- and angle-resolved photoemission spectroscopy

We study dynamics of incoherent exciton formation under interband photoexcitation in Cu$_2$O using time-and angle-resolved photoemission spectroscopy at 90 K. Hot electrons injected by allowed optical transitions with 3.40-eV photons show ultrafast relaxation to the conduction-band minimum (CBM), surviving up to 500 fs after excitation. While hot-electron states with high excess energy show a rapid population decay of ~25 fs, an abrupt increase to 130 fs is observed for states with excess energies of 0.15 eV. This latter is interpreted in terms of phonon bottleneck dynamics characteristic of LO-phonon mediated energy relaxation. Excitons, having a small binding energy of 60 meV, are formed below the CBM quasi-instantaneously and subsequently relax to the 1S-exciton state of the yellow series within 1.5 ps. We find that, together with possible plasma screening for electron-hole interaction, the cooling of exciton center-of-mass motion plays an important role in the exciton relaxation dynamics. The characteristic features of exciton photoionization process are critically discussed based on the detailed analysis of angle-resolved photoemission results for the 1S excitons formed 1.5 ps after excitation.

cond-mat.mes-hall↗

arXiv2019

Spin-orbit entangled j=1/2 moments in Ba$_2$CeIrO$_6$ -- a frustrated fcc quantum magnet

We establish the double perovskite Ba$_2$CeIrO$_6$ as a nearly ideal model system for j=1/2 moments, with resonant inelastic x-ray scattering indicating a deviation of less than 1% from the ideally cubic j=1/2 state. The local j=1/2 moments form an fcc lattice and are found to order antiferromagnetically at $T_N$=14K, more than an order of magnitude below the Curie-Weiss temperature. Model calculations show that the geometric frustration of the fcc Heisenberg antiferromagnet is further enhanced by a next-nearest neighbor exchange, indicated by ab initio theory. Magnetic order is driven by a bond-directional Kitaev exchange and by local distortions via a strong magneto-elastic effect - both effects are typically not expected for j=1/2 compounds making Ba2CeIrO6 a riveting example for the rich physics of spin-orbit entangled Mott insulators.

cond-mat.str-el↗

arXiv2019

High-Field Quantum Disordered State in $α$-RuCl3: Spin Flips, Bound States, and a Multi-Particle Continuum

Layered $α$-RuCl3 has been discussed as a proximate Kitaev spin liquid compound. Raman and THz spectroscopy of magnetic excitations confirm that the low-temperature antiferromagnetic ordered phase features a broad Raman continuum, together with two magnon-like excitations at 2.7 and 3.6 meV, respectively. The continuum strength is maximized as long-range order is suppressed by an external magnetic field. The state above the field-induced quantum phase transition around 7.5 T is characterized by a gapped multi-particle continuum out of which a two-particle bound state emerges, together with a well-defined single-particle excitation at lower energy. Exact diagonalization calculations demonstrate that Kitaev and off-diagonal exchange terms in the Fleury-Loudon operator are crucial for the occurrence of these features in the Raman spectra. Our study firmly establishes the partially-polarized quantum disordered character of the high-field phase.

cond-mat.str-el↗

arXiv2019

Inelastic light scattering in the spin cluster Mott insulator Cu$_{2}$OSeO$_{3}$

Clusters of single spins form the relevant spin entities in the formation of long-range magnetic order in spin cluster Mott insulators. Such type of spin order bears resemblance to molecular crystals, and we therefore may expect a prototypical spin wave spectrum which can be divided into low-energy external and high-energy internal cluster spin wave modes. Here, we study high-energy spin cluster excitations in the spin cluster Mott insulator Cu$_{2}$OSeO$_{3}$ by means of spontaneous Raman scattering. Multiple high-energy optical magnon modes are observed, of which the Raman-activity is shown to originate in the Elliot-Loudon scattering mechanism. Upon crossing the long-range ordering transition temperature the magnetic modes significantly broaden, corresponding to scattering from localized spin excitations within the spin clusters. Different optical phonon modes show a strong temperature dependence, evidencing a strong magnetoelectric coupling between optical phonons and the high-energy spin cluster excitations. Our results support the picture that Cu$_{2}$OSeO$_{3}$ can be regarded as a solid-state molecular crystal of spin nature.

cond-mat.str-el↗