Tomographic reconstruction of oxygen orbitals in lithium-rich battery materials.

The electrification of heavy-duty transport and aviation will require new strategies to increase the energy density of electrode materials1,2. The use of anionic redox represents one possible approach to meeting this ambitious target. However, questions remain regarding the validity of the O2-/O- oxygen redox paradigm, and alternative explanations for the origin of the anionic capacity have been proposed3, because the electronic orbitals associated with redox reactions cannot be measured by standard experiments. Here, using high-energy X-ray Compton measurements together with first-principles modelling, we show how the electronic orbital that lies at the heart of the reversible and stable anionic redox activity can be imaged and visualized, and its character and symmetry determined. We find that differential changes in the Compton profile with lithium-ion concentration are sensitive to the phase of the electronic wave function, and carry signatures of electrostatic and covalent bonding effects4. Our study not only provides a picture of the workings of a lithium-rich battery at the atomic scale, but also suggests pathways to improving existing battery materials and designing new ones.

New insight into impact of humidity on direct air capture performance by SIFSIX-3-Cu MOF.

Removal of CO2 from air is one of the key human challenges in battling global warming. SIFSIX-3-Cu is a promising metal-organic framework (MOF) suggested for carbon capture even at low CO2 concentrations. However, the impact of humidity on its performance in direct air capture (DAC) is poorly understood. To evaluate the MOF performance for DAC application under humid conditions, we investigate the adsorption of H2O, CO2, and N2 using density functional theory (DFT), grand canonical Monte Carlo (GCMC), and molecular dynamics (MD) simulations. The simulation results show a higher tendency of SIFSIX-3-Cu towards H2O adsorption rather than CO2 (and N2). The results agree with the adsorption isotherms for the pure compounds from the Sips model. The extended Sips model shows 1.34 mmol g-1 CO2 adsorption at the atmospheric pressure and 298 K for the CO2/N2 mixture containing 400 ppm CO2, and low CO2 adsorption (less than 0.75 mmol g-1) at a low relative humidity (RH) of 20%. This finding highlights the efficiency of SIFSIX-3-Cu for DAC in dry air and the negative impact of humidity on the CO2 selective adsorption. Therefore, we suggest to consider the impairing of humidity effects when designing a SIFSIX-3-Cu-based CO2 separation process and removal of any water vapor before introduction of the air to SIFSIX-3-Cu.

Comparing first-principles density functionals plus corrections for the lattice dynamics of YBa2Cu3O6.

The enigmatic mechanism underlying unconventional high-temperature superconductivity, especially the role of lattice dynamics, has remained a subject of debate. Theoretical insights have long been hindered due to the lack of an accurate first-principles description of the lattice dynamics of cuprates. Recently, using the r2SCAN meta-generalized gradient approximation (meta-GGA) functional, we have been able to achieve accurate phonon spectra of an insulating cuprate YBa2Cu3O6 and discover significant magnetoelastic coupling in experimentally interesting Cu-O bond stretching optical modes [Ning et al., Phys. Rev. B 107, 045126 (2023)]. We extend this work by comparing Perdew-Burke-Ernzerhof and r2SCAN performances with corrections from the on-site Hubbard U and the D4 van der Waals (vdW) methods, aiming at further understanding on both the materials science side and the density functional side. We demonstrate the importance of vdW and self-interaction corrections for accurate first-principles YBa2Cu3O6 lattice dynamics. Since r2SCAN by itself partially accounts for these effects, the good performance of r2SCAN is now more fully explained. In addition, the performances of the Tao-Mo series of meta-GGAs, which are constructed in a different way from the strongly constrained and appropriately normed (SCAN) meta-GGA and its revised version r2SCAN, are also compared and discussed.

First-Principles Perspective on Gas Adsorption by [Fe4S4]-Based Metal-Organic Frameworks.

[Fe4S4] or [4S-4Fe] clusters are responsible for storing and transferring electrons in key cellular processes and interact with their microenvironment to modulate their oxidation and magnetic states. Therefore, these clusters are ideal for the metal node of chemically and electromagnetically tunable metal-organic frameworks (MOFs). To examine the adsorption-based applications of [Fe4S4]-based MOFs, we used density functional theory calculations and studied the adsorption of CO2, CH4, H2O, H2, N2, NO2, O2, and SO2 onto [Fe4S4]0, [Fe4S4]2+, and two 1D MOF models with the carboxylate and 1,4-benzenedithiolate organic linkers. Our reaction kinetics and thermodynamics results indicated that MOF formation promotes the oxidative and hydrolytic stability of the [Fe4S4] clusters but decreases their adsorption efficiency. Our study suggests the potential industrial applications of these [Fe4S4]-based MOFs because of their limited capacity to adsorb CO2, CH4, H2O, H2, N2, O2, and SO2 and high selectivity for NO2 adsorption.

Competing stripe and magnetic phases in the cuprates from first principles.

Realistic description of competing phases in complex quantum materials has proven extremely challenging. For example, much of the existing density-functional-theory-based first-principles framework fails in the cuprate superconductors. Various many-body approaches involve generic model Hamiltonians and do not account for the interplay between the spin, charge, and lattice degrees of freedom. Here, by deploying the recently constructed strongly constrained and appropriately normed (SCAN) density functional, we show how the landscape of competing stripe and magnetic phases can be addressed on a first-principles basis both in the parent insulator YBa2Cu3O6 and the near-optimally doped YBa2Cu3O7 as archetype cuprate compounds. In YBa2Cu3O7, we find many stripe phases that are nearly degenerate with the ground state and may give rise to the pseudogap state from which the high-temperature superconducting state emerges. We invoke no free parameters such as the Hubbard U, which has been the basis of much of the existing cuprate literature. Lattice degrees of freedom are found to be crucially important in stabilizing the various phases.

Photoemission Spectroscopy Using Virtual Photons Emitted by Positron Sticking: A Complementary Probe for Top-Layer Surface Electronic Structures.

We present a spectroscopic method which utilizes virtual photons to selectively measure the electronic structure of the topmost atomic layer. These virtual photons are created when incident positrons transition from vacuum states to bound surface states on the sample surface and can transfer sufficient energy to excite electrons into the vacuum. The short interaction range of the virtual photons restricts the penetration depth to approximately the Thomas-Fermi screening length. Measurements and analysis of the kinetic energies of the emitted electrons made on a single layer of graphene deposited on Cu and on the clean Cu substrate show that the ejected electrons originate exclusively from the topmost atomic layer. Moreover, we find that the kinetic energies of the emitted electrons reflect the density of states at the surface. These results demonstrate that this technique will be a complementary tool to existing spectroscopic techniques in determining the electronic structure of 2D materials and fragile systems due to the absence of subsurface contributions and probe-induced surface damage.

Re-examining the giant magnetization density in α''-Fe16N2 with the SCAN+U method.

We present an in-depth discussion of the magnetic ground state of α''-Fe16N2 within the framework of the density functional theory (DFT). The exchange-correlation effects are treated using a variety of schemes, including the local-spin-density approximation, the generalized-gradient approximation, and the Strongly-Constrained-and-Appropriately-Normed (SCAN) scheme. We also delineate effects of adding an on-site interaction parameter U on the Fe sites. Among all the schemes considered, only SCAN+U is found to capture the surprisingly large magnetization density in α''-Fe16N2 that has been observed experimentally. Our study shows how the combination of SCAN and self-interaction corrections applied on different Fe sites through the parameter U can reproduce both the correct equilibrium volume and the giant magnetization density of α''-Fe16N2.

Nature of the Positron State in CdSe Quantum Dots.

Previous studies have shown that positron-annihilation spectroscopy is a highly sensitive probe of the electronic structure and surface composition of ligand-capped semiconductor quantum dots (QDs) embedded in thin films. The nature of the associated positron state, however, whether the positron is confined inside the QDs or localized at their surfaces, has so far remained unresolved. Our positron-annihilation lifetime spectroscopy studies of CdSe QDs reveal the presence of a strong lifetime component in the narrow range of 358-371 ps, indicating abundant trapping and annihilation of positrons at the surfaces of the QDs. Furthermore, our ab initio calculations of the positron wave function and lifetime employing a recent formulation of the weighted density approximation demonstrate the presence of a positron surface state and predict positron lifetimes close to experimental values. Our study thus resolves the long-standing question regarding the nature of the positron state in semiconductor QDs and opens the way to extract quantitative information on surface composition and ligand-surface interactions of colloidal semiconductor QDs through highly sensitive positron-annihilation techniques.

Proposed parameter-free model for interpreting the measured positron annihilation spectra of materials using a generalized gradient approximation.

Positron annihilation spectroscopy is often used to analyze the local electronic structure of materials of technological interest. Reliable theoretical tools are crucial to interpret the measured spectra. Here, we propose a parameter-free gradient correction scheme for a local-density approximation obtained from high-quality quantum Monte Carlo data. The results of our calculations compare favorably with positron affinity and lifetime measurements, opening new avenues for highly precise and advanced positron characterization of materials.

Why LiFePO4 is a safe battery electrode: Coulomb repulsion induced electron-state reshuffling upon lithiation.

LiFePO4 is a battery cathode material with high safety standards due to its unique electronic structure. We performed systematic experimental and theoretical studies based on soft X-ray emission, absorption, and hard X-ray Raman spectroscopy of LixFePO4 nanoparticles and single crystals. The results clearly show a non-rigid electron-state reconfiguration of both the occupied and unoccupied Fe-3d and O-2p states during the (de)lithiation process. We focus on the energy configurations of the occupied states of LiFePO4 and the unoccupied states of FePO4, which are the critical states where electrons are removed and injected during the charge and discharge process, respectively. In LiFePO4, the soft X-ray emission spectroscopy shows that, due to the Coulomb repulsion effect, the occupied Fe-3d states with the minority spin sit close to the Fermi level. In FePO4, the soft X-ray absorption and hard X-ray Raman spectroscopy show that the unoccupied Fe-3d states again sit close to the Fermi level. These critical 3d electron state configurations are consistent with the calculations based on modified Becke and Johnson potentials GGA+U (MBJGGA+U) framework, which improves the overall lineshape prediction compared with the conventionally used GGA+U method. The combined experimental and theoretical studies show that the non-rigid electron state reshuffling guarantees the stability of oxygen during the redox reaction throughout the charge and discharge process of LiFePO4 electrodes, leading to the intrinsic safe performance of the electrodes.

Quantum view of Li-ion high mobility at carbon-coated cathode interfaces.

Lithium-ion batteries (LIBs) are among the most promising power sources for electric vehicles, portable electronics and smart grids. In LIBs, the cathode is a major bottleneck, with a particular reference to its low electrical conductivity and Li-ion diffusivity. The coating with carbon layers is generally employed to enhance the electrical conductivity and to protect the active material from degradation during operation. Here, we demonstrate that this layer has a primary role in the lithium diffusivity into the cathode nanoparticles. Positron is a useful quantum probe at the electroactive materials/carbon interface to sense the mobility of Li-ion. Broadband electrical spectroscopy demonstrates that only a small number of Li-ions are moving, and that their diffusion strongly depends on the type of carbon additive. Positron annihilation and broadband electrical spectroscopies are crucial complementary tools to investigate the electronic effect of the carbon phase on the cathode performance and Li-ion dynamics in electroactive materials.

Phase transformation and lithiation effect on electronic structure of Li(x)FePO4: an in-depth study by soft X-ray and simulations.

Through soft X-ray absorption spectroscopy, hard X-ray Raman scattering, and theoretical simulations, we provide the most in-depth and systematic study of the phase transformation and (de)lithiation effect on electronic structure in Li(x)FePO(4) nanoparticles and single crystals. Soft X-ray reveals directly the valence states of Fe 3d electrons in the vicinity of Fermi level, which is sensitive to the local lattice distortion, but more importantly offers detailed information on the evolution of electronic states at different electrochemical stages. The soft X-ray spectra of Li(x)FePO(4) nanoparticles evolve vividly with the (de)lithiation level. The spectra fingerprint the (de)lithiation process with rich information on Li distribution, valency, spin states, and crystal field. The high-resolution spectra reveal a subtle but critical deviation from two-phase transformation in our electrochemically prepared samples. In addition, we performed both first-principles calculations and multiplet simulations of the spectra and quantitatively determined the 3d valence states that are completely redistributed through (de)lithiation. This electronic reconfiguration was further verified by the polarization-dependent spectra collected on LiFePO(4) single crystals, especially along the lithium diffusion direction. The evolution of the 3d states is overall consistent with the local lattice distortion and provides a fundamental picture of the (de)lithiation effects on electronic structure in the Li(x)FePO(4) system.

Structural properties of PbTe quantum dots revealed by high-energy x-ray diffraction.

High-energy X-ray diffraction (HE-XRD) experiments combined with an analysisbased on atomic-pair-distribution functions can be an effective tool for probing low-dimensional materials. Here, we show how such an analysis can be used to gain insightinto structural properties of PbTe nanoparticles. We interpret our HE-XRD data using anorthorhombic Pnma phase of PbTe, which is an orthorhombic distortion of the rocksalt phase.Although local crystal geometry can vary substantially with particle size at scales below 10 nm,and for very small nanoparticles the particle size itself influences X-ray diffraction patterns,our study shows that HE-XRD can provide a unique nano-characterization tool for unravelingstructural properties of nanoscale systems.

Bacteriorhodopsin Enhances Efficiency of Perovskite Solar Cells.

Recently, halide perovskites have upstaged decades of solar cell development by reaching power conversion efficiencies that surpass the performance of polycrystalline silicon. The efficiency improvement in the perovskite cells is related to repeated recycling between photons and electron-hole pairs, reduced recombination losses, and increased carrier lifetimes. Here, we demonstrate a novel approach toward augmenting the perovskite solar cell efficiency by invoking the Förster Resonance Energy Transfer (FRET) mechanism. FRET occurs in the near-field region as the bacteriorhodopsin (bR) protein, and perovskite has similar optical gaps. Titanium dioxide functionalized with the bR protein is shown to accelerate the electron injection from excitons produced in the perovskite layer. FRET predicts the strength of long-range excitonic transport between the perovskite and bR layers. Solar cells incorporating TiO2/bR layers are found to exhibit much higher photovoltaic performance as compared to baseline cells without bR. These results open the opportunity to develop a new class of bioperovskite solar cells with improved performance and stability.

Visualizing redox orbitals and their potentials in advanced lithium-ion battery materials using high-resolution x-ray Compton scattering.

Reduction-oxidation (redox) reactions are the key processes that underlie the batteries powering smartphones, laptops, and electric cars. A redox process involves transfer of electrons between two species. For example, in a lithium-ion battery, current is generated when conduction electrons from the lithium anode are transferred to the redox orbitals of the cathode material. The ability to visualize or image the redox orbitals and how these orbitals evolve under lithiation and delithiation processes is thus of great fundamental and practical interest for understanding the workings of battery materials. We show that inelastic scattering spectroscopy using high-energy x-ray photons (Compton scattering) can yield faithful momentum space images of the redox orbitals by considering lithium iron phosphate (LiFePO4 or LFP) as an exemplar cathode battery material. Our analysis reveals a new link between voltage and the localization of transition metal 3d orbitals and provides insight into the puzzling mechanism of potential shift and how it is connected to the modification of the bond between the transition metal and oxygen atoms. Our study thus opens a novel spectroscopic pathway for improving the performance of battery materials.

Understanding the magnetic interaction between intrinsic defects and impurity ions in room-temperature ferromagnetic Mg1-xFexO thin films.

Understanding the nature and characteristics of the intrinsic defects and impurities in the dielectric barrier separating the ferromagnetic electrodes in a magnetic tunneling junction is of great importance for understanding the often observed 'barrier-breakdown' therein. In this connection, we present herein systematic experimental (SQUID and synchrotron-radiation-based x-ray absorption spectroscopy) and computational studies on the electronic and magnetic properties of Mg1-xFexO thin films. Our studies reveal: (i) defect aggregates comprised of basic and trimer units (Fe impurity coupled to 1 or 2 Mg vacancies) and (ii) existence of two competing magnetic orders, defect- and dopant-induced, with spin densities aligning anti-parallel if the trimer is present in the oxide matrix. These findings open up new avenues for designing tunneling barriers with high endurance and tunneling effect upon tuning the concentration/distribution of the two magnetic orders.

Experimental Observation of Redox-Induced Fe-N Switching Behavior as a Determinant Role for Oxygen Reduction Activity.

The commercialization of electrochemical energy conversion and storage devices relies largely upon the development of highly active catalysts based on abundant and inexpensive materials. Despite recent achievements in this respect, further progress is hindered by the poor understanding of the nature of active sites and reaction mechanisms. Herein, by characterizing representative iron-based catalysts under reactive conditions, we identify three Fe-N4-like catalytic centers with distinctly different Fe-N switching behaviors (Fe moving toward or away from the N4-plane) during the oxygen reduction reaction (ORR), and show that their ORR activities are essentially governed by the dynamic structure associated with the Fe(2+/3+) redox transition, rather than the static structure of the bare sites. Our findings reveal the structural origin of the enhanced catalytic activity of pyrolyzed Fe-based catalysts compared to nonpyrolyzed Fe-macrocycle compounds. More generally, the fundamental insights into the dynamic nature of transition-metal compounds during electron-transfer reactions will potentially guide rational design of these materials for broad applications.

Engineering a Robust Photovoltaic Device with Quantum Dots and Bacteriorhodopsin.

We present a route toward a radical improvement in solar cell efficiency using resonant energy transfer and sensitization of semiconductor metal oxides with a light-harvesting quantum dot (QD)/bacteriorhodopsin (bR) layer designed by protein engineering. The specific aims of our approach are (1) controlled engineering of highly ordered bR/QD complexes; (2) replacement of the liquid electrolyte by a thin layer of gold; (3) highly oriented deposition of bR/QD complexes on a gold layer; and (4) use of the Forster resonance energy transfer coupling between bR and QDs to achieve an efficient absorbing layer for dye-sensitized solar cells. This proposed approach is based on the unique optical characteristics of QDs, on the photovoltaic properties of bR, and on state-of-the-art nanobioengineering technologies. It permits spatial and optical coupling together with control of hybrid material components on the bionanoscale. This method paves the way to the development of the solid-state photovoltaic device with the efficiency increased to practical levels.

Energy transfer performance of mechanical nanoresonators coupled with electromagnetic fields.

: We study the energy transfer performance in electrically and magnetically coupled mechanical nanoresonators. Using the resonant scattering theory, we show that magnetically coupled resonators can achieve the same energy transfer performance as for their electrically coupled counterparts or even outperform them within the scale of interest. Magnetic and electric coupling are compared in the nanotube radio, a realistic example of a nano-scale mechanical resonator. The energy transfer performance is also discussed for a newly proposed bio-nanoresonator composed of magnetosomes coated with a net of protein fibers.

Efficient magnetic torque transduction in biological environments using tunable nanomechanical resonators.

Electromagnetic interactions with biological systems promise new possibilities in medical applications and synthetic biology. Creating a controlled action in biological systems requires an efficient transduction of the electromagnetic energy to thermal or mechanical biosignals. In this paper, we present the design and optimization for a nano-scale magnetic torque transducer based on a tunable nanomechanical resonator. Operating in the resonance regime allows the presented system to efficiently absorb a large amount of energy from the source. In addition, systems tuned on well separated resonance frequencies may operate simultaneously without any interference. We describe the theoretical model of the system and show the possibility of achieving the resonance in biological settings for a system with reasonable dimensions.