The Lorenz ratio as a guide to scattering contributions to transport in strongly correlated metals.

In many physical situations in which many-body assemblies exist at temperature T, a characteristic quantum-mechanical time scale of approximately [Formula: see text] can be identified in both theory and experiment, leading to speculation that it may be the shortest meaningful time in such circumstances. This behavior can be investigated by probing the scattering rate of electrons in a broad class of materials often referred to as "strongly correlated metals". It is clear that in some cases only electron-electron scattering can be its cause, while in others it arises from high-temperature scattering of electrons from quantized lattice vibrations, i.e., phonons. In metallic oxides, which are among the most studied materials, analysis of electrical transport does not satisfactorily identify the relevant scattering mechanism at "high" temperatures near room temperature. We therefore employ a contactless optical method to measure thermal diffusivity in two Ru-based layered perovskites, Sr3Ru2O7 and Sr2RuO4, and use the measurements to extract the dimensionless Lorenz ratio. By comparing our results to the literature data on both conventional and unconventional metals, we show how the analysis of high-temperature thermal transport can both give important insight into dominant scattering mechanisms and be offered as a stringent test of theories attempting to explain anomalous scattering.

Characterizing Local Electronic States of Twin Boundaries in Copper.

Grain boundaries (GBs) and twin boundaries (TBs) in copper (Cu) are two major planar defects that influence electrical conductivity due to their complex electron transport characteristics, involving electron scattering and electron concentration. Understanding their local electronic states is crucial for the design of future conductor materials. In this study, we characterized electron behaviors at TBs and GBs within one Cu grain using atomic force microscopy. Our findings revealed that, compared with GBs, TBs exhibit better current transport capability (direct-current mode) and larger electromagnetic loss (high-frequency microwave mode). Both kelvin probe force microscopy and theoretical analysis suggested that TBs with smaller lattice disorder possess lower density of states at the Fermi level. The reduced density of states may result in decreased electron scattering and a lower electron concentration at TBs. The latter can be highlighted by the high-frequency skinning effect, manifested as larger electromagnetic loss and weaker high-frequency conductivity.

Extracting the electronic structure signal from X-ray and electron scattering in the gas phase.

X-ray and electron scattering from free gas-phase molecules is examined using the independent atom model (IAM) and ab initio electronic structure calculations. The IAM describes the effect of the molecular geometry on the scattering, but does not account for the redistribution of valence electrons due to, for instance, chemical bonding. By examining the total, i.e. energy-integrated, scattering from three molecules, fluoroform (CHF3), 1,3-cyclohexadiene (C6H8) and naphthalene (C10H8), the effect of electron redistribution is found to predominantly reside at small-to-medium values of the momentum transfer (q ≤ 8 Å-1) in the scattering signal, with a maximum percent difference contribution at 2 ≤ q ≤ 3 Å-1. A procedure to determine the molecular geometry from the large-q scattering is demonstrated, making it possible to more clearly identify the deviation of the scattering from the IAM approximation at small and intermediate q and to provide a measure of the effect of valence electronic structure on the scattering signal.

Benchmarking the ideal sample thickness in cryo-EM.

The relationship between sample thickness and quality of data obtained is investigated by microcrystal electron diffraction (MicroED). Several electron microscopy (EM) grids containing proteinase K microcrystals of similar sizes from the same crystallization batch were prepared. Each grid was transferred into a focused ion beam and a scanning electron microscope in which the crystals were then systematically thinned into lamellae between 95- and 1,650-nm thick. MicroED data were collected at either 120-, 200-, or 300-kV accelerating voltages. Lamellae thicknesses were expressed in multiples of the corresponding inelastic mean free path to allow the results from different acceleration voltages to be compared. The quality of the data and subsequently determined structures were assessed using standard crystallographic measures. Structures were reliably determined with similar quality from crystalline lamellae up to twice the inelastic mean free path. Lower resolution diffraction was observed at three times the mean free path for all three accelerating voltages, but the data quality was insufficient to yield structures. Finally, no coherent diffraction was observed from lamellae thicker than four times the calculated inelastic mean free path. This study benchmarks the ideal specimen thickness with implications for all cryo-EM methods.

Synergistic Effect of Electron Scattering and Space Charge Transfer Enabled Unprecedented Room Temperature NO2 Sensing Response of SnO2.

Metal oxide gas sensors have long faced the challenge of low response and poor selectivity, especially at room temperature (RT). Herein, a synergistic effect of electron scattering and space charge transfer is proposed to comprehensively improve gas sensing performance of n-type metal oxides toward oxidizing NO2 (electron acceptor) at RT. To this end, the porous SnO2 nanoparticles (NPs) assembled from grains of about 4 nm with rich oxygen vacancies are developed through an acetylacetone-assisted solvent evaporation approach combined with precise N2 and air calcinations. The results show that the as-fabricated porous SnO2 NPs sensor exhibits an unprecedented NO2 -sensing performance, including outstanding response (Rg /Ra  = 772.33 @ 5 ppm), fast recovery (<2 s), an extremely low detection limit (10 ppb), and exceptional selectivity (response ratio >30) at RT. Theoretical calculation and experimental tests confirm that the excellent NO2 sensing performance is mainly attributed to the unique synergistic effect of electron scattering and space charge transfer. This work proposes a useful strategy for developing high-performance RT NO2 sensors using metal oxides, and provides an in-depth understanding for the basic characteristics of the synergistic effect on gas sensing, paving the way for efficient and low power consumption gas detection at RT.

Electron Scattering from 1-Methyl-5-Nitroimidazole: Cross-Sections for Modeling Electron Transport through Potential Radiosensitizers.

In this study, we present a complete set of electron scattering cross-sections from 1-Methyl-5-Nitroimidazole (1M5NI) molecules for impact energies ranging from 0.1 to 1000 eV. This information is relevant to evaluate the potential role of 1M5NI as a molecular radiosensitizers. The total electron scattering cross-sections (TCS) that we previously measured with a magnetically confined electron transmission apparatus were considered as the reference values for the present analysis. Elastic scattering cross-sections were calculated by means of two different schemes: The Schwinger multichannel (SMC) method for the lower energies (below 15 eV) and the independent atom model-based screening-corrected additivity rule with interferences (IAM-SCARI) for higher energies (above 15 eV). The latter was also applied to calculate the total ionization cross-sections, which were complemented with experimental values of the induced cationic fragmentation by electron impact. Double differential ionization cross-sections were measured with a reaction microscope multi-particle coincidence spectrometer. Using a momentum imaging spectrometer, direct measurements of the anion fragment yields and kinetic energies by the dissociative electron attachment are also presented. Cross-sections for the other inelastic channels were derived with a self-consistent procedure by sampling their values at a given energy to ensure that the sum of the cross-sections of all the scattering processes available at that energy coincides with the corresponding TCS. This cross-section data set is ready to be used for modelling electron-induced radiation damage at the molecular level to biologically relevant media containing 1M5NI as a potential radiosensitizer. Nonetheless, a proper evaluation of its radiosensitizing effects would require further radiobiological experiments.

Formation of Temporary Negative Ions and Their Subsequent Fragmentation upon Electron Attachment to CoQ0 and CoQ0 H2.

Ubiquinone molecules have a high biological relevance due to their action as electron carriers in the mitochondrial electron transport chain. Here, we studied the dissociative interaction of free electrons with CoQ0 , the smallest ubiquinone derivative with no isoprenyl units, and its fully reduced form, 2,3-dimethoxy-5-methylhydroquinone (CoQ0 H2 ), an ubiquinol derivative. The anionic products produced upon dissociative electron attachment (DEA) were detected by quadrupole mass spectrometry and studied theoretically through quantum chemical and electron scattering calculations. Despite the structural similarity of the two studied molecules, remarkably only a few DEA reactions are present for both compounds, such as abstraction of a neutral hydrogen atom or the release of a negatively charged methyl group. While the loss of a neutral methyl group represents the most abundant reaction observed in DEA to CoQ0 , this pathway is not observed for CoQ0 H2 . Instead, the loss of a neutral OH radical from the CoQ0 H2 temporary negative ion is observed as the most abundant reaction channel. Overall, this study gives insights into electron attachment properties of simple derivatives of more complex molecules found in biochemical pathways.

How optical excitation controls the structure and properties of vanadium dioxide.

We combine ultrafast electron diffraction and time-resolved terahertz spectroscopy measurements to link structure and electronic transport properties during the photoinduced insulator-metal transitions in vanadium dioxide. We determine the structure of the metastable monoclinic metal phase, which exhibits antiferroelectric charge order arising from a thermally activated, orbital-selective phase transition in the electron system. The relative contribution of the photoinduced monoclinic and rutile metals to the time-dependent and pump-fluence-dependent multiphase character of the film is established, as is the respective impact of these two distinct phase transitions on the observed changes in terahertz conductivity. Our results represent an important example of how light can control the properties of strongly correlated materials and demonstrate that multimodal experiments are essential when seeking a detailed connection between ultrafast changes in optical-electronic properties and lattice structure.

Modeling Auger Processes with Nonadiabatic Molecular Dynamics.

Auger-type energy exchange plays key roles in the carrier dynamics in nanomaterials due to strong carrier-carrier interactions. However, theoretical descriptions are limited to perturbative calculations of scattering rates on static structures. We develop an accurate and efficient ab initio technique to model Auger scattering with nonadiabatic molecular dynamics. We incorporate the many-body Coulomb matrix into several surface hopping methods and describe simultaneously charge-charge and charge-phonon scattering in the time-domain and in a nonperturbative, configuration-dependent manner. The approach is illustrated with a CdSe quantum dot. Auger scattering between electrons and holes breaks the phonon bottleneck to electron relaxation. The bottleneck is recovered when electrons and holes are decoupled. The simulations correctly reproduce all experimental processes and time scales, including Auger- and phonon-assisted cooling of hot electrons, intraband carrier relaxation, and carrier recombination. Providing detailed insights into the energy flow, the developed method allows studies of carrier dynamics in nanomaterials with strong carrier-carrier interactions.

The Strong Enhancement of Electron-Impact Ionization Processes in Dense Plasma by Transient Spatial Localization.

Recent experiments have observed much higher electron-ion collisional ionization cross sections and rates in dense plasmas than predicted by the current standard atomic collision theory, including the plasma screening effect. We suggest that the use of (distorted) plane waves for incident and scattered electrons is not adequate to describe the dissipation that occurs during the ionization event. Random collisions with free electrons and ions in plasma cause electron matter waves to lose their phase, which results in the partial decoherence of incident and scattered electrons. Such a plasma-induced transient spatial localization of the continuum electron states significantly modifies the wave functions of continuum electrons, resulting in a strong enhancement of the electron-ion collisional ionization of ions in plasma compared to isolated ions. Here, we develop a theoretical formulation to calculate the differential and integral cross sections by incorporating the effects of plasma screening and transient spatial localization. The approach is then used to investigate the electron-impact ionization of ions in solid-density magnesium plasma, yielding results that are consistent with experiments. In dense plasma, the correlation of continuum electron energies is modified, and the integral cross sections and rates increase considerably. For the ionization of Mg9+e+1s22s2S→1s21S+2e, the ionization cross sections increase several-fold, and the rates increase by one order of magnitude. Our findings provide new insight into collisional ionization and three-body recombination and may aid investigations of the transport properties and nonequilibrium evolution of dense plasma.

Attosecond Photoionization Dynamics: from Molecules over Clusters to the Liquid Phase.

Photoionization is a process taking place on attosecond time scales. How its properties evolve from isolated particles to the condensed phase is an open question of both fundamental and practical relevance. Here, we review recent work that has advanced the study of photoionization dynamics from atoms to molecules, clusters and the liquid phase. The first measurements of molecular photoionization delays have revealed the attosecond dynamics of electron emission from a molecular shape resonance and their sensitivity to the molecular potential. Using electron-ion coincidence spectroscopy these measurements have been extended from isolated molecules to clusters. A continuous increase of the delays with the water-cluster size has been observed up to a size of 4-5 molecules, followed by a saturation towards larger clusters. Comparison with calculations has revealed a correlation of the time delay with the spatial extension of the created electron hole. Using cylindrical liquid-microjet techniques, these measurements have also been extended to liquid water, revealing a delay relative to isolated water molecules that was very similar to the largest water clusters studied. Detailed modeling based on Monte-Carlo simulations confirmed that these delays are dominated by the contributions of the first two solvation shells, which agrees with the results of the cluster measurements. These combined results open the perspective of experimentally characterizing the delocalization of electronic wave functions in complex systems and studying their evolution on attosecond time scales.

Photoemission from Free Particles and Droplets.

Intriguing properties of photoemission from free, unsupported particles and droplets were predicted nearly 50 years ago, though experiments were a technical challenge. The last few decades have seen a surge of research in the field, due to advances in aerosol technology (generation, characterization, and transfer into vacuum), the development of photoelectron imaging spectrometers, and advances in vacuum ultraviolet and ultrafast light sources. Particles and droplets offer several advantages for photoemission studies. For example, photoemission spectra are dependent on the particle's size, shape, and composition, providing a wealth of information that allows for the retrieval of genuine electronic properties of condensed phase. In this review, with a focus on submicrometer-sized, dielectric particles and droplets, we explain the utility of photoemission from such systems, summarize several applications from the literature, and present some thoughts on future research directions.

A Fast Algorithm for Scanning Transmission Electron Microscopy Imaging and 4D-STEM Diffraction Simulations.

Scanning transmission electron microscopy (STEM) is an extremely versatile method for studying materials on the atomic scale. Many STEM experiments are supported or validated with electron scattering simulations. However, using the conventional multislice algorithm to perform these simulations can require extremely large calculation times, particularly for experiments with millions of probe positions as each probe position must be simulated independently. Recently, the plane-wave reciprocal-space interpolated scattering matrix (PRISM) algorithm was developed to reduce calculation times for large STEM simulations. Here, we introduce a new method for STEM simulation: partitioning of the STEM probe into "beamlets," given by a natural neighbor interpolation of the parent beams. This idea is compatible with PRISM simulations and can lead to even larger improvements in simulation time, as well requiring significantly less computer random access memory (RAM). We have performed various simulations to demonstrate the advantages and disadvantages of partitioned PRISM STEM simulations. We find that this new algorithm is particularly useful for 4D-STEM simulations of large fields of view. We also provide a reference implementation of the multislice, PRISM, and partitioned PRISM algorithms.

Double and Triple Differential Cross Sections for Single Ionization of Benzene by Electron Impact.

Experimental results for the electron impact ionization of benzene, providing double (DDCS) and triple differential cross sections (TDCS) at the incident energy of 90 eV, measured with a multi-particle momentum spectrometer, are reported in this paper. The most intense ionization channel is assigned to the parent ion (C6H6+) formation. The DDCS values are presented for three different transferred energies, namely 30, 40 and 50 eV. The present TDCS are given for two fixed values of the ejected electron energy (E2), at 5 and 10 eV, and an electron scattering angle (θ1) of 10°. Different features related to the molecular orbitals of benzene from where the electron is extracted are observed. In addition, a semi-empirical formula to be used as the inelastic angular distribution function in electron transport simulations has been derived from the present DDCS result and compared with other expressions available in the literature.

A Complete Cross Section Data Set for Electron Scattering by Pyridine: Modelling Electron Transport in the Energy Range 0-100 eV.

Electron scattering cross sections for pyridine in the energy range 0-100 eV, which we previously measured or calculated, have been critically compiled and complemented here with new measurements of electron energy loss spectra and double differential ionization cross sections. Experimental techniques employed in this study include a linear transmission apparatus and a reaction microscope system. To fulfill the transport model requirements, theoretical data have been recalculated within our independent atom model with screening corrected additivity rule and interference effects (IAM-SCAR) method for energies above 10 eV. In addition, results from the R-matrix and Schwinger multichannel with pseudopotential methods, for energies below 15 eV and 20 eV, respectively, are presented here. The reliability of this complete data set has been evaluated by comparing the simulated energy distribution of electrons transmitted through pyridine, with that observed in an electron-gas transmission experiment under magnetic confinement conditions. In addition, our representation of the angular distribution of the inelastically scattered electrons is discussed on the basis of the present double differential cross section experimental results.

Doubly-Charged Negative Ions as Novel Tunable Catalysts: Graphene and Fullerene Molecules Versus Atomic Metals.

The fundamental mechanism underlying negative-ion catalysis involves bond-strength breaking in the transition state (TS). Doubly-charged atomic/molecular anions are proposed as novel dynamic tunable catalysts, as demonstrated in water oxidation into peroxide. Density Functional Theory TS calculations have found a tunable energy activation barrier reduction ranging from 0.030 eV to 2.070 eV, with Si2-, Pu2-, Pa2- and Sn2- being the best catalysts; the radioactive elements usher in new application opportunities. C602- significantly reduces the standard C60- TS energy barrier, while graphene increases it, behaving like cationic systems. According to their reaction barrier reduction efficiency, variation across charge states and systems, rank-ordered catalysts reveal their tunable and wide applications, ranging from water purification to biocompatible antiviral and antibacterial sanitation systems.

Electron collisions with atoms, ions, molecules, and surfaces: Fundamental science empowering advances in technology.

Electron collisions with atoms, ions, molecules, and surfaces are critically important to the understanding and modeling of low-temperature plasmas (LTPs), and so in the development of technologies based on LTPs. Recent progress in obtaining experimental benchmark data and the development of highly sophisticated computational methods is highlighted. With the cesium-based diode-pumped alkali laser and remote plasma etching of Si3N4 as examples, we demonstrate how accurate and comprehensive datasets for electron collisions enable complex modeling of plasma-using technologies that empower our high-technology-based society.

Enhanced Electron Scattering upon Ion Relocation in BaVS3 at 69 K.

The present study deals with the anomalous heat capacity peak and thermal conductivity of BaVS 3 near the metal-insulator transition present at 69 K. The transition is related to a structural transition from an orthorhombic to monoclinic phase. Heat capacity measurements at this temperature exhibit a significant and relatively broad peak, which is also sample dependent. The present study calculates the entropy increase during the structural transition and we show that the additional entropy is caused by enhanced electron scattering as a result of the structural reorientation of the nuclei. Within the model it is possible to explain quantitatively the observed peak alike structure in the heat capacity and in heat conductivity.

Photocurrent Switching of Monolayer MoS2 Using a Metal-Insulator Transition.

We achieve switching on/off the photocurrent of monolayer molybdenum disulfide (MoS2) by controlling the metal-insulator transition (MIT). N-type semiconducting MoS2 under a large negative gate bias generates a photocurrent attributed to the increase of excess carriers in the conduction band by optical excitation. However, under a large positive gate bias, a phase shift from semiconducting to metallic MoS2 is caused, and the photocurrent by excess carriers in the conduction band induced by the laser disappears due to enhanced electron-electron scattering. Thus, no photocurrent is detected in metallic MoS2. Our results indicate that the photocurrent of MoS2 can be switched on/off by appropriately controlling the MIT transition by means of gate bias.

A few selected contributions to electron and photon collisions with H2 and H 2 + .

We discuss a number of aspects regarding the physics of H 2 + and H2. This includes low-energy electron scattering processes and the interaction of both weak (perturbative) and strong (ultrafast/intense) electromagnetic radiation with those systems.