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At least 19 records

Ultra-high resolution electron microscopy

The last two decades have seen dramatic advances in the resolution of the electron microscope brought about by the successful correction of lens aberrations that previously limited resolution for most of its history. Here we briefly review these advances, the achievement of sub-Ångstrom resolution and the ability to identify individual atoms, their bonding configurations and even their dynamics and diffusion pathways. We then present a review of the basic physics of electron scattering, lens aberrations and their correction, and an approximate imaging theory for thin crystals which provides physical insight into the various different imaging modes. Then we proceed to describe a more exact imaging theory starting from Yoshioka’s formulation and covering full image simulation methods using Bloch waves, the multislice formulation and the frozen phonon/quantum excitation of phonons models. Delocalization of inelastic scattering has become an important limiting factor at atomic resolution. We therefore discuss this issue extensively, showing how the full-width-half-maximum is the appropriate measure for predicting image contrast, but the diameter containing 50% of the excitation is an important measure of the range of the interaction. These two measures can differ by a factor of 5, are not a simple function of binding energy, and full image simulations are required to match to experiment. The Z-dependence of annular dark field images is also discussed extensively, both for single atoms and for crystals, and we show that temporal incoherence must be included accurately if atomic species are to be identified through matching experimental intensities to simulations. Finally we mention a few promising directions for future investigation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Quantum Tunneling of Water in Beryl. A New State of the Water Molecule

When using neutron scattering and ab initio simulations, we document the discovery of a new “quantum tunneling state” of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. We observed a number of peaks in the inelastic neutron scattering spectra that were uniquely assigned to water quantum tunneling. Additionally, the water proton momentum distribution was measured with deep inelastic neutron scattering, which directly revealed coherent delocalization of the protons in the ground state.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Inelastic and deep inelastic neutron spectroscopy of water molecules under ultra-confinement

Water confined within sub-nanometer channels of silicate minerals presents an extreme case of confinement, where the restricted molecules are situated in channels whose diameter is not much larger than the water molecule itself. Recently, we discovered a new quantum tunneling state of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. Several peaks were observed in the inelastic neutron scattering (INS) spectra which were uniquely assigned to water quantum tunnelling. In addition, the water proton momentum distribution measured with deep inelastic neutron scattering (DINS) at 4.3 K directly showed coherent delocalization of the water protons in the ground state. The obtained average kinetic energy (EK ) of the water protons was found to be ~30% less than it is in bulk liquid water and ice phases. In the current work we present INS and DINS study of water in single crystal beryl in wider temperature range, T=5–260 K, where we observed significant increase of EK of the confined water protons with temperature increase. The obtained INS data also indicate that with increasing temperature water molecules are progressively involved in hydrogen bonding (HB) with the beryl cage, while HB is almost absent at low temperatures.

Kolesnikov, Alexander I.↗

Pressure-Driven Changes in the Electronic Bonding Environment of GeO 2 Glass above Megabar Pressures

Noncrystalline oxides under pressure undergo gradual structural modifications, highlighted by the formation of a dense noncrystalline network topology. The nature of the densified networks and their electronic structures at high pressures may account for the mechanical hardening and the anomalous changes in electromagnetic properties. Despite its importance, direct probing of the electronic structures in amorphous oxides under compression above the Mbar pressure (>100 GPa) is currently lacking. Here, we report the observation of pressure-driven changes in electronic configurations and their delocalization around oxygen in glasses using inelastic X-ray scattering spectroscopy (IXS). In particular, the first O K-edge IXS spectra for compressed GeO 2 glass up to 148 GPa, the highest pressure ever reached in an experimental study of GeO 2 glass, reveal that the glass densification results from a progressive increase of oxygen proximity. While the triply coordinated oxygen [3] O is dominant below ~50 GPa, the IXS spectra resolve multiple edge features that are unique to topologically disordered [4] O upon densification above 55 GPa. Topological compaction in GeO 2 glass above 100 GPa results in pronounced electronic delocalization, revealing the contribution from Ge d-orbitals to oxide densification. Strong correlations between the glass density and the electronic configurations beyond the Mbar conditions highlight the electronic origins of densification of heavy-metal-bearing oxide glasses. Furthermore, current experimental breakthroughs shed light on the direct probing of the electronic density of states in high-Z oxides above 1 Mbar, offering prospects for studies on the pressure-driven changes in magnetism, superconductivity, and electronic transport properties in heavy-metal-bearing oxides under compression.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic magnetic response across the pressure-induced structural phase transition in CeNi

We report that the intermediate-valence compound CeNi experiences a pressure-induced first-order structural phase transition with an abrupt change in the unit cell volume, and as such constitutes an attractive system to study pressure-driven f-electron delocalization behavior in a system with an unstable f-electron shell. The inelastic neutron scattering study of the dynamic magnetic response of CeNi reveals that the structural transition increases the characteristic energy of magnetic fluctuations due to enhanced Ce 4f–Ni 3d hybridization. At the same time, the inelastic 4f magnetic form factor remains unchanged.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Quasimolecular 𝐽 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. Here, 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 tet = 3/2 moments. The modulation of the RIXS intensity as function of the transferred momentum q allows us to determine the cluster wave function, which depends on competing intracluster hopping terms that mix states with different character. This mixed wave function 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 wave function, tunable via intracluster hopping, opens a new perspective on the large family of lacunar spinels and cluster Mott insulators in general.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Charge carrier dynamics in two-dimensional hybrid perovskites: Dion–Jacobson vs. Ruddlesden–Popper phases

Two-dimensional (2D) halide perovskites are promising materials for environmentally stable next-generation optoelectronic device applications. Besides the widely investigated Ruddlesden–Popper (RP) phases, Dion–Jacobson (DJ) phases are attracting considerable attention due to their rapid emergence as efficient solar cell materials. However, there is very little atomistic understanding of the charge carrier dynamics under ambient conditions for these DJ-phases, limiting the possibilities to tune their optoelectronic performances through compositional engineering routes. In this study, by combining nonadiabatic molecular dynamics with time-domain density functional theory methods at room temperature, we compare the dominant non-radiative carrier recombination and dephasing processes in RP and DJ monolayered lead halide perovskites. Our systematic study demonstrates that performance-limiting nonradiative carrier recombination processes greatly depends on the electron–phonon interactions induced by structural fluctuations and instantaneous charge localization in these materials. The stiffer interlayer packing due to the presence of single spacer dications, which separates the lead iodide slabs, reduces the thermal fluctuations in the DJ-phase to a greater extent than that in the RP-phase 2D-perovskites. Specific electronic coupling between the closely spaced lead iodide layers enhances the delocalization of band-edge charge densities in DJ-phase systems. Compared to the RP-phase, reduced inelastic electron–phonon scattering in DJ-phase perovskites significantly limits intrinsic non-radiative recombination processes. The consequent enhancement in the photogenerated charge carrier lifetime makes DJ-phase perovskites potentially suitable for various optoelectronic devices. The computational insights gained from this study allow us to outline a set of robust design principles for DJ-phase perovskites to strategically tune their optoelectronic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced hybridization in the electronic ground state of the intercalated honeycomb iridate Ag 3 LiIr 2 O 6

In this work, we use x-ray spectroscopy at the Ir L 3 /L 2 absorption edge to study powder samples of the intercalated honeycomb magnet Ag 3 LiIr 2 O 6 . Based on x-ray absorption and resonant inelastic x-ray scattering measurements, and exact diagonalization calculations including nearest-neighbor Ir-Ir electron hopping integrals, we argue that the intercalation of Ag atoms results in a delocalized electronic structure with enhanced Ir-O hybridization, departing from the local relativistic j eff =1/2 state. We find that the relative orbital contribution to the magnetic moment is increased and the magnetization density is spatially extended and asymmetric in this hybridized state. Our results confirm the importance of metal-ligand hybridization in the magnetism of transition metal oxides and provide empirical guidance for understanding the collective magnetism in intercalated honeycomb iridates.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Direct Detection of Dimer Orbitals in Ba 5 AlIr 2 O 11

The electronic states of many Mott insulators, including iridates, are often conceptualized in terms of localized atomic states such as the famous "${J}_{\mathrm{eff}}=1/2$ state." Although orbital hybridization can strongly modify such states and dramatically change the electronic properties of materials, probing this process is highly challenging. We directly detect and quantify the formation of dimer orbitals in an iridate material ${\mathrm{Ba}}_{5}{\mathrm{AlIr}}_{2}{\mathrm{O}}_{11}$ using resonant inelastic x-ray scattering. Sharp peaks corresponding to the excitations of dimer orbitals are observed and analyzed by a combination of density functional theory calculations and theoretical simulations based on an Ir-Ir cluster model. Such partially delocalized dimer states lead to a redefinition of the angular momentum of the electrons and changes in the magnetic and electronic behaviors of the material. We use this to explain the reduction of the observed magnetic moment with respect to predictions based on atomic states. This study opens new directions to study dimerization in a large family of materials, including solids, heterostructures, molecules, and transient states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electronic Configurational Transformation of Network Modifiers in Aluminate Glass above Megabar Pressures

Electronic responses of glasses under extreme pressures differ from those of crystalline analogs. Their distinct electronic environments are found in network formers with well-defined, covalent-bonded coordination environments (e.g., [4] Si and [4] Al) and in network modifiers with more disordered, ionic-bonded configurations (e.g., [5,6,7] Ca). Deciphering the evolution of the bonding environment of network modifier cations upon compression provides atomic insights into the pressure-driven hardening and transport properties of glasses. Despite the importance, in contrast to extensive efforts to uncover how network formers behave under pressure, considerable structural disorder around network modifiers makes it challenging to probe their electronic bonding environments under compression. Our understanding of the evolution of network modifiers above megabars is currently absent. Here, we report a discovery of highly densified electronic configurations of network modifier Ca in aluminate glass under extreme compression via the first inelastic X-ray scattering at the Ca L-edge up to 140 GPa. As evidenced by the prominent pressure-driven increases in electronic dispersion and delocalization, densified calcium environments are characterized by a decreased average Ca–O distance, the formation of highly coordinated calcium, a broader distribution of topological variables, and a greater distortion of Ca polyhedra above megabars. The spectral features for the Ca environments reveal significant electronic and bonding modifications, including pressure-driven increases in the ligand field interaction, the covalence characteristic of the Ca–O bond, and the electron–hole Coulomb interaction. These densification paths identify the electronic adaptation of network modifiers above megabars, shedding light on the origins of enhanced electron transport and the electron-storing capacity of glasses under pressure.

amorphous materials↗

Revealing the electronic structure of LiC 6 by soft X-ray spectroscopy

The electronic structure of LiC 6 has been investigated in this paper by soft X-ray absorption and emission spectroscopies. The results reveal that upon full lithiation of graphite, the Li 2s electrons are transferred into the carbon π* states in a near rigid-band behavior, resulting in the increased density of states near E F and the shift of σ* states to lower energies. Finally, in addition, the resonant inelastic X-ray scattering spectra of LiC 6 do not show strong dispersive features as that of graphite, indicating that the crystal momentum is not conserved during the scattering process due to the delocalization of electrons in the intermediate state.

36 MATERIALS SCIENCE↗

The nature of frontier orbitals under systematic ligand exchange in (pseudo-)octahedral Fe( ii ) complexes

Understanding and controlling properties of transition metal complexes is a crucial step towards tailoring materials for sustainable energy applications. In a systematic approach, we use resonant inelastic X-ray scattering to study the influence of ligand substitution on the valence electronic structure around an aqueous iron(II) center. Exchanging cyanide with 2-2'-bipyridine ligands reshapes frontier orbitals in a way that reduces metal 3d charge delocalization onto the ligands. This net decrease of metal–ligand covalency results in lower metal-centered excited state energies in agreement with previously reported excited state dynamics. Furthermore, traces of solvent-effects were found indicating a varying interaction strength of the solvent with ligands of different character. Lastly, our results demonstrate how ligand exchange can be exploited to shape frontier orbitals of transition metal complexes in solution-phase chemistry; insights upon which future efforts can built when tailoring the functionality of photoactive systems for light-harvesting applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

From antiferromagnetic and hidden order to Pauli paramagnetism in U M 2 Si 2 compounds with 5 f electron duality

Using inelastic X-ray scattering beyond the dipole limit and hard X-ray photoelectron spectroscopy we establish the dual nature of the U 5 f electrons in U M 2 Si 2 ( M = Pd, Ni, Ru, Fe), regardless of their degree of delocalization. We have observed that the compounds have in common a local atomic-like state that is well described by the U 5 f 2 configuration with the $Γ^{(1)}_1$ and $Γ_2$ quasi-doublet symmetry. The amount of the U 5 f 3 configuration, however, varies considerably across the U M 2 Si 2 series, indicating an increase of U 5 f itineracy in going from M = Pd to Ni to Ru and to the Fe compound. The identified electronic states explain the formation of the very large ordered magnetic moments in UPd 2 Si 2 and UNi 2 Si 2 , the availability of orbital degrees of freedom needed for the hidden order in URu 2 Si 2 to occur, as well as the appearance of Pauli paramagnetism in UFe 2 Si 2 . A unified and systematic picture of the U M 2 Si 2 compounds may now be drawn, thereby providing suggestions for additional experiments to induce hidden order and/or superconductivity in U compounds with the tetragonal body-centered ThCr 2 Si 2 structure.

36 MATERIALS SCIENCE↗

Probing the Boundary between Classical and Quantum Mechanics by Analyzing the Energy Dependence of Single-Electron Scattering Events at the Nanoscale

The relation between the energy-dependent particle and wave descriptions of electron–matter interactions on the nanoscale was analyzed by measuring the delocalization of an evanescent field from energy-filtered amplitude images of sample/vacuum interfaces with a special aberration-corrected electron microscope. The spatial field extension coincided with the energy-dependent self-coherence length of propagating wave packets that obeyed the time-dependent Schrödinger equation, and underwent a Goos–Hänchen shift. The findings support the view that wave packets are created by self-interferences during coherent–inelastic Coulomb interactions with a decoherence phase close to Δφ = 0.5 rad. Due to a strictly reciprocal dependence on energy, the wave packets shrink below atomic dimensions for electron energy losses beyond 1000 eV, and thus appear particle-like. Consequently, our observations inevitably include pulse-like wave propagations that stimulate structural dynamics in nanomaterials at any electron energy loss, which can be exploited to unravel time-dependent structure–function relationships on the nanoscale.

36 MATERIALS SCIENCE↗

Imaging of the electronic bonding of diamond at pressures up to 2 million atmospheres

Diamond shows unprecedented hardness. Because hardness is a measure of resistance of chemical bonds in a material to external indentation, the electronic bonding nature of diamond beyond several million atmospheres is key to understanding the origin of hardness. However, probing the electronic structures of diamond at such extreme pressure has not been experimentally possible. The measurements on the inelastic x-ray scattering spectra for diamond up to 2 million atmospheres provide data on the evolution of its electronic structures under compression. The mapping of the observed electronic density of states allows us to obtain a two-dimensional image of the bonding transitions of diamond undergoing deformation. The spectral change near edge onset is minor beyond a million atmospheres, while its electronic structure displays marked pressure-induced electron delocalization. Such electronic responses indicate that diamond’s external rigidity is supported by its ability to reconcile internal stress, providing insights into the origins of hardness in materials.

36 MATERIALS SCIENCE↗

Combining microscopic and macroscopic probes to untangle the single-ion anisotropy and exchange energies in an S = 1 quantum antiferromagnet [Combining micro- and macroscopic probes to untangle single-ion and spatial exchange anisotropies in a S = 1 quantum antiferromagnet]

The magnetic ground state of the quasi-one-dimensional spin-1 antiferromagnetic chain is sensitive to the relative sizes of the single-ion anisotropy (D) and the intrachain (J) and interchain (J') exchange interactions. The ratios D/J and J' /J dictate the material's placement in one of three competing phases: a Haldane gapped phase, a quantum paramagnet, and an XY-ordered state, with a quantum critical point at their junction. We have identified [Ni(HF 2 )(pyz) 2 ] SbF 6 , where pyz = pyrazine, as a rare candidate in which this behavior can be explored in detail. Combining neutron scattering (elastic and inelastic) in applied magnetic fields of up to 10 tesla and magnetization measurements in fields of up to 60 tesla with numerical modeling of experimental observables, we are able to obtain accurate values of all of the parameters of the Hamiltonian [D = 13.3(1) K, J = 10.4(3) K, and J' = 1.4(2) K], despite the polycrystalline nature of the sample. Density-functional theory calculations result in similar couplings (J = 9.2 K, J' = 1.8 K) and predict that the majority of the total spin population resides on the Ni(II) ion, while the remaining spin density is delocalized over both ligand types. Finally, the general procedures outlined in this paper permit phase boundaries and quantum-critical points to be explored in anisotropic systems for which single crystals are as yet unavailable.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

X-ray spectroscopic characterization of Co(IV) and metal–metal interactions in Co 4 O 4 : Electronic structure contributions to the formation of high-valent states relevant to the oxygen evolution reaction

In this paper, the formation of high-valent states is a key factor in making highly active transition metal-based catalysts of the oxygen-evolving reaction (OER). These high oxidation states will be strongly influenced by the local geometric and electronic structures of the metal ion, which is difficult to study due to spectroscopically active and complex backgrounds, short lifetimes, and limited concentrations. Here, we use a wide range of complementary X-ray spectroscopies coupled to DFT calculations to study Co 4 O 4 cubanes, which provide insight into the high-valent Co(IV) centers responsible for the activity of molecular and heterogeneous OER catalysts. The combination of X-ray absorption and 1s3p resonant inelastic X-ray scattering (Kβ RIXS) allow Co(IV) to be isolated and studied against a spectroscopically active Co(III) background. Co K- and L-edge X-ray absorption data allow for a detailed characterization of the 3d-manifold of effectively localized Co(IV) centers and provide a direct handle on the ligand field environment and covalency of the t 2g -based redox active molecular orbital. Kβ RIXS is also shown to provide a powerful probe of Co(IV), and specific spectral features are sensitive to the degree of oxo-mediated metal-metal coupling across Co 4 O 4 . Guided by the data, calculations show electron-hole delocalization can actually oppose Co(IV) formation. Computational extension of Co 4 O 4 to CoM 3 O 4 structures (M = redox-inactive metal) defines electronic structure contri-butions to Co(IV) formation. Redox activity is shown to be linearly related to covalency, and M(III) oxo inductive effects on Co(IV) oxo bonding can tune the covalency of high-valent sites over a large range and thereby tune E 0 over hundreds of mVs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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 d d 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 d d excitations. Here we study the impact of charge transfer and magnetic order on the excitation spectrum of the nickel dihalides ( Ni X 2 , X = Cl , Br, and I) using Ni- L 3 edge 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 nonlocal interactions of on-site d d excitations with the surrounding crystal or 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 d d excitations in charge-transfer insulators. Published by the American Physical Society 2024

2-dimensional systems↗