Atomic States Research Articles

A multi-orbital Hund´s rules-based Ionic Hamiltonian for transition metal atoms: High-order Equation of Motion Method approach and Kondo resonances.

A multi-orbital ionic Hamiltonian is presented to analyze the many-body properties of the d-transition metal atoms. This Hamiltonian considers all the atomic states obeying the first Hund´s rule and also includes all orbital degeneracy, as well as the interaction of the atom with a metal. We analyze the solution of this ionic Hamiltonian by means of the Equation of Motion (EOM) method up to the fourth order, V4, in the atom-metal interaction. Equations for the appropriate Green-functions for analyzing the chemical and transport properties of the system are given for different atom occupancies. In particular, we introduce a full analysis of the multi-orbital Hamiltonian including atomic configurations with N, N+1 and N-1 electrons, and discuss its Kondo properties. The shells d1, d2 and d3 are analyzed in detail and Kondo energies are deduced in all these cases showing good agreement with the conventional known results.&#xD.

Regulating the Ni-O bond length by constructing Ni(OH)2/CNTs heterostructure for enhanced nucleophile electrocatalytic oxidation

The electro-driven generation of the active Ni(OH)O species is crucial for the Ni(OH)2 to efficiently drive the nucleophilic oxidation reaction. However, the strategy to facilitate the generation of the Ni(OH)O species is only limited to the construction of the Pt/Ni(OH)2 heterostructures. In this study, carbon nanotubes (CNTs) are employed to reduce the dehydrogenation energy of the Ni(OH)2 by constructing Ni(OH)2/60CNTs heterostructures. The CNTs shorten the Ni-O bond length and increase the valence state of Ni atoms in Ni(OH)2, thus highly promoting the generation of Ni(OH)O. When the Ni(OH)2/60CNTs heterostructure is used for urea oxidation reaction, it displays highly enhanced catalytic activity relative to pure Ni(OH)2, attaining a current density of 10 mA cm−2 at 1.36 V versus reversible hydrogen electrode. This work provides a new strategy for reducing the dehydrogenation energy of the Ni(OH)2 and will inspire more research work on the recognition of the impact of metal–oxygen bond length on NOR activity.

The singlet S-wave resonances of He atom in dense quantum plasmas

The singlet S-wave resonances of the He atom embedded in dense quantum plasmas are investigated by applying the complex-coordinate rotation method. The modified Debye–Hückel potential is used to model the effective interactions of the test atom in a dense quantum plasma environment. The explicitly correlated Hylleraas configuration-interaction basis function is employed to take into account the electron correlation effect. The first ten S-wave resonance states of the He atom below the N = 2 thresholds of the He+ ion are calculated, and the resonance energies and widths at a variety of screening parameters are obtained with high accuracy. The plasma screening effect on the expectation values of the radial and angular physical quantities are analyzed for the first time.

Enhanced optical pumping using mutually orthogonal magnetic fields for quantum sensing

The atomic population trapped in irrelevant atomic states is a limiting factor for sensors based on laser-atom interaction. Using a bi-chromatic light field along with a specific combination of magnetic fields, we show a significant increase in the amplitude (i.e., more than seven times) of a two-photon coherent population trapping (CPT) resonance, which can be effectively used for atomic magnetometry. This increase in amplitude can be explained through enhanced optical pumping via the transfer of population to the relevant Zeeman states. Our experimental observations are consistent with the theoretical calculations carried out for a realistic three-level atomic system using density matrix formalism. We further discuss the optimum condition for enhanced optical pumping by adjusting the ground-state decoherence rate. Enhanced optical pumping through the manipulation of the magnetic field is quite important and is of great interest in the field of quantum technology.

Effect of Annealing Temperature on Microstructure and Magnetocaloric Properties of Gd-Based Metallic Microfibers

In this paper, vacuum annealing has been adopted to introduce atomic cluster micro-regions inside Gd-based metallic microfibers to further explore the effect of the structural changes on the magnetocaloric properties and the mechanism which is systematically expressed. The experimental results indicate that the as-prepared Gd-based metallic microfibers have favorable amorphous formation ability and thermal stability. After annealing @ 380 °C, the maximum magnetic entropy change −ΔSmmax, refrigerating capacity (RC), and relative cooling power (RCP) values of the Gd-based metallic microfibers are 7.20 J/kg·K, 459.4 J/kg, and 588.7 J/kg, respectively. Combined with the transmission electron microscopy analysis results, the internal organizational order of the annealed microfibers is significantly altered, and the atomic clusters formed in localized regions, which reduce the magnetocrystalline anisotropy of the microfibers. While under the uni-action of an external magnetic field, the magnetic moment rotation state and magnetic domain structure distribution of the micro-region atoms will be changed obviously, thereby changing the general magnetic properties and magnetocaloric properties of the metallic microfibers. The above research results can promote the engineering application of Gd-based metallic microfibers in the field of magnetic refrigeration.

Effect of Cu incorporation in silicate and modified borate bioglass materials for health applications: insights from synchrotron-based x-ray absorption spectroscopy

This contribution investigates the effect of variable copper incorporation (x = 0.2, 1.0, 2.0, and 4.0) in silicate (45 SiO2, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) and modified borate (45 B2O3, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) bioglass materials to be used for bone bonding applications. X-ray absorption fine structure spectroscopy (XAFS) has been used to determine the oxidation states and local coordination structure of Cu atoms in silicate-based and borate-based glasses at the Cu K-edge (~ 8979 eV). The oxidation states of Cu atoms have been determined by near-edge XAFS (XANES) fingerprinting employing reference standard compounds of Cu. Cu (I) and Cu (II) XANES spectra of the standard reference compounds were linearly combined to fit the normalized μ(E) data of the collected XANES spectra using linear combination fitting (LCF approach). The obtained results prove that most of the silicate glass samples contain Cu2O almost exclusively, while modified borate glass samples contain a significant mixture of Cu2O and CuO phases. According to the literature, the remarkable coexistence of Cu2O and CuO phases within the borate sample, particularly when x = 4, promotes the conversion process to allow the more facile formation of hydroxy carbonate apatite (HCA). The best fit structural parameters derived from extended-XAFS (EXAFS) fitting show that the ratio between Cu (I) and Cu (II) in borate glass agreed well with that extracted from XANES analysis. XANES and EXAFS conclude that borate glass with x = 4 is the most suitable composition for bone bonding applications.

Ab initio simulation of the dynamic shock response of single crystal and lightweight multicomponent alloy

The dynamic response of shock wave impact on single crystal aluminium and lightweight multicomponent alloy Al-Cu-Li-Mg is simulated by using the combination of Ab initio Molecular Dynamics (AIMD) and Multi-Scale Shock Technique (MSST), with the analysis carried out at the atomic/electronic levels. The simulation is verified by comparing the particle velocity of single crystal obtained in this work with the data in literature. The shock compression process not only involves the migration of atoms, but also is related to electronic transition. Two stages could be found in the shock compression process: oscillatory compression of the crystal cell and oscillatory migration of the atoms. The crystal structure of the multicomponent alloy could be disordered even at low shock speed, due to the difference in the ability to migrate between different kinds of atoms. As the sample is shock-compressed, the contribution proportion of crystal orbitals shows a sharp decrease for D orbital, while it increases significantly for S orbital and P orbital. The electron structure shows a quicker response to the shock wave compression process than the crystal structure. The orbital contribution from P orbital of the crystal is mainly due to the P orbital of Al atoms, while the orbital contribution from D orbital of the crystal is mainly due to the D orbital of Cu atoms. Total Density of States (TDOS) is mainly contributed by the Projected Density of State (PDOS) of Cu atoms in the occupied state of energy levels, while it is close to the PDOS of Al atoms in the non-occupied state of energy levels.

Diffraction of polar molecules at nanomasks with low charge density

The wave nature of matter is a cornerstone of modern physics and has been demonstrated for a wide range of fundamental and composite particles. While diffraction at nanomechanical masks is usually regarded to be independent of internal atomic or molecular states, the particles' polarizabilities and dipole moments lead to dispersive interactions with the grating surface. In prior experiments, such forces largely prevented coherent diffraction of polar molecules as they induce dephasing of the matter wave in the presence of randomly distributed charges inside the grating. Here, we show that surface milling using neon ions facilitates the fabrication of lowly charged nanomasks in gold-capped silicon nitride membranes. This allows us to observe diffraction of polar molecules with over four times larger electric dipole moment than in previous experiments, opening a path towards distinction of structural conformers in matter-wave experiments. Published by the American Physical Society 2024

Floquet geometric entangling gates in ground-state manifolds of Rydberg atoms

We propose new applications of Floquet theory in Rydberg atoms for constructing quantum entangling gates in atomic ground-state manifolds. By dynamically periodically modulating the Rabi frequencies of transitions between ground and Rydberg states of atoms, error-resilient two-qubit entangling gates can be implemented in the regime of Rydberg blockade. According to different degrees of Floquet theory utilization, the fidelity of the resulting controlled gates surpasses that of the original reference, and it exhibits high robustness against Rabi error in two qubits and detuning error in the control qubit. Our method only uses encoding in the ground states, and compared to the original scheme using Rydberg state for encoding, it is less susceptible to environmental interference, making it more practical to implement. Therefore, our approach may have broader applications or potential for further expansion of geometric quantum computation with neutral atoms.

A Fundamental Correlative Spectroscopic Study on Li1‐xNiO2 and NaNiO2

AbstractThe intricate relationship between local atomic arrangements and electronic states significantly influences the electrochemical properties of Li‐ion battery cathode materials. Despite decades of investigation, a consensus regarding the local atomic and electronic structure of LiNiO2 remains elusive. This ambiguity stems from the potential distortion of Ni sites, either via Jahn‐Teller (JT) distortion or bond disproportionation (BD), complicating the understanding of the charge compensation mechanism involving Ni and O. This study compares the structures of LiNiO2 and NaNiO2, a JT system, using an innovative approach that integrates bulk spectroscopy techniques on standardized interoperable samples for enhanced reliability. While X‐r and theoretical calculations fail to differentiate between the proposed scenarios, Raman spectroscopy highlights local structural distinctions between monoclinic NaNiO2 and rhombohedral LiNiO2. HAXPES confirms various formal oxidation states for Ni, supported by RIXS data indicating 3d8 states, emphasizing negative charge transfer from Ni and some bond disproportionation in LiNiO2. Regarding charge compensation, XRS and RIXS suggest oxygen hole involvement in redox activity, whereas Raman spectroscopy does not detect molecular oxygen. This comprehensive spectroscopic analysis highlights the importance of correlative characterization workflows in elucidating complex structural‐electrochemical relationships.

Nanomechanically-induced nonequilibrium quantum phase transition to a self-organized density wave of a Bose-Einstein condensate

We report on a nonequilibrium quantum phase transition (NQPT) in a hybrid quantum many-body system consisting of a vibrational mode of a damped nanomembrane interacting optomechanically with a cavity, whose output light couples to two internal states of an ultracold Bose gas held in an external quasi-one-dimensional box potential. For small effective membrane-atom couplings, the system is in a homogeneous Bose-Einstein condensate (BEC) steady state, with no membrane displacement. Depending on the transition frequency between the two internal atomic states, either one or both internal states are occupied. By increasing the atom-membrane couplings, the system transitions to a symmetry-broken self-organized BEC phase, which is characterized by a considerably displaced membrane steady-state and density-wave-like BEC profiles. This NQPT can be both discontinuous and continuous for a certain interval of transition frequencies and is purely discontinuous outside of it. Published by the American Physical Society 2024

An integrated atom array-nanophotonic chip platform with background-free imaging

Arrays of neutral atoms trapped in optical tweezers have emerged as a leading platform for quantum information processing and quantum simulation due to their scalability, reconfigurable connectivity, and high-fidelity operations. Individual atoms are promising candidates for quantum networking due to their capability to emit indistinguishable photons that are entangled with their internal atomic states. Integrating atom arrays with photonic interfaces would enable distributed architectures in which nodes hosting many processing qubits could be efficiently linked together via the distribution of remote entanglement. However, many atom array techniques cease to work in close proximity to photonic interfaces, with atom detection via standard fluorescence imaging presenting a major challenge due to scattering from nearby photonic devices. Here, we demonstrate an architecture that combines atom arrays with up to 64 optical tweezers and a millimeter-scale photonic chip hosting more than 100 nanophotonic cavities. We achieve high-fidelity ( ~ 99.2%), background-free imaging in close proximity to nanofabricated cavities using a multichromatic excitation and detection scheme. The atoms can be imaged while trapped a few hundred nanometers above the dielectric surface, which we verify using Stark shift measurements of the modified trapping potential. Finally, we rearrange atoms into defect-free arrays and load them simultaneously onto the same or multiple devices.

Geometric properties of the first singlet S-wave excited state of two-electron atoms near the critical nuclear charge

Abstract In this work the geometric structure parameters and radial density distribution of 1s2s 1 S excited state of the two-electron atomic system near the critical nuclear charge Z c were calculated in detail under tripled Hylleraas basis set. Contrary to the localized behavior observed in the ground and the doubly excited 2p 2 3 P e states, for this state our results identify that while the behavior of the inner electron increasingly resembles that of a hydrogen-like atomic system, the outer electron in the excited state exhibits diffused hydrogen-like character and becomes perpendicular to the inner electron as nuclear charge Z approaches Z c. This study provides insights into the electronic structure and stability of the two-electron system in the vicinity of the critical nuclear charge.

Charge Transfer in He+ - He → He(1s4l, l ≥ 2) - He+ Collisions in Intermediate Energy Range.

The anticrossing spectra of the helium line λ1s4l D3,F-1s2p P3=447.2 nm emitted after electron capture by He+ ions in He+-He collisions were measured for projectile energies of 10-29 keV. Furthermore, considering the excited states' time evolution, the theoretical intensity functions were calculated. The electric field and density distributions of the target He atoms in the collision volume were taken into account, and by fitting the theoretical intensities to the measured ones, the post-collisional states of the charge-transferred He atoms were determined. The results indicate that for the intermediate projectile energy range, the electronic charge distributions were asymmetric, but the electric dipole moments did not change, as in the case of the target atoms excited directly in the collisions. This result shows that the Paul trap mechanism may play an important role in the charge transfer excitation in this energy range.

X‐ray standing wave assisted XANES for depth dependent chemical state analysis of Cr in Cr2O3/Cr bilayer structure

We report the detailed depth‐dependent structural and chemical analysis of the Cr2O3/Cr bilayer structure deposited on Si ˂100˃ substrate. The non‐destructive simultaneous X‐ray reflectivity and grazing incidence X‐ray fluorescence measurements were used for this purpose. Corresponding variation in the chemical state of Cr atoms as a function of depth has been studied using X‐ray standing wave (XSW) assisted X‐ray absorption near edge structure (XANES) measurements. Various oxidation states of Cr atoms present in the Cr2O3/Cr bilayer structure were determined using X‐ray photoelectron spectroscopy (XPS). Depth‐resolved XANES measurements confirmed the presence of chromium oxide (Cr2O3) and hydroxide (Cr (OH)3) at the top surface of the Cr2O3/Cr bilayer structure. The results also reveal the presence of metallic Cr along with its compounds Cr2O3 and Cr (OH)3 at the interface medium, showing significant mixing between the Cr2O3 and Cr layers. Our results clearly demonstrate that the XSW assisted XANES technique is extremely efficient for determining the variation of chemical states at the surface, interface, and different depths of a thin film structure. Such types of analysis are particularly useful for differentiating the presence of a metal from its own oxides, even at higher depths inside a thin film medium.

Theoretical study on the synergistic mechanism of Fe–Mn in sodium-ion batteries

This article conducts first-principles calculations to initially explore the construction of two configurations, NaFeO2 (NFO) and NaMnO2 (NMO), and studies the mixing enthalpies under different Fe–Mn ratios. The results indicate that NaFe3/8Mn5/8O2 (NFMO) exhibits the most thermodynamically stable structure. Subsequent calculations on the mixing enthalpies and volume changes during the sodium extraction process for NFO, NMO, and NFMO configurations are presented, along with the partial density of states (PDOS) and Bader charges of transition metals (TM) and oxygen. These calculations reveal the synergistic mechanism of Fe and Mn. Fe and Mn can engage in more complex electron exchanges during sodium extraction, optimizing the internal electron density distribution and overall charge balance, thereby stabilizing the crystal structure and reducing the migration of Fe3+ to the sodium layers during deep sodium extraction. The interaction between Fe’s 3d electrons and Mn’s 3d electrons through the shared oxygen atoms’ 2p orbitals occurs in the Fe–Mn–O network. This interaction can lead to a rebalancing of the electron density around Mn³⁺ atoms, mitigating the asymmetric electron density distribution caused by the d4 configuration of the lone Mn³⁺ and suppressing the Jahn-Teller effect of Mn3+. Moreover, the synergistic effects between Fe and Mn can provide a more balanced charge distribution, reducing extreme changes to the charge state of oxygen atoms and decreasing the irreversible oxygen release caused by anionic redox reactions during deep sodium extraction, thereby enhancing the material’s stability. This in-depth study of the interaction mechanism at the microscopic level when co-doping Fe and Mn offers valuable insights for the rational design and development of high-performance cathode materials.

Impact of Quantum Non-Locality and Electronic Non-Ideality on the Shannon Entropy for Atomic States in Dense Plasma.

The influence of the collective and quantum effects on the Shannon information entropy for atomic states in dense nonideal plasma was investigated. The interaction potential, which takes into account the effect of quantum non-locality as well as electronic correlations, was used to solve the Schrödinger equation for the hydrogen atom. It is shown that taking into account ionic screening leads to an increase in entropy, while taking into account only electronic screening does not lead to significant changes.

Highly Selective Electrocatalytic CO2 Conversion to Tailored Products through Precise Regulation of Hydrogenation and C-C Coupling.

The electrochemical reduction reaction of carbon dioxide (CO2RR) into valuable products offers notable economic benefits and contributes to environmental sustainability. However, precisely controlling the reaction pathways and selectively converting key intermediates pose considerable challenges. In this study, our theoretical calculations reveal that the active sites with different states of copper atoms (1-3-5-7-9) play a pivotal role in the adsorption behavior of the *CHO critical intermediate. This behavior dictates the subsequent hydrogenation and coupling steps, ultimately influencing the formation of the desired products. Consequently, we designed two model electrocatalysts comprising Cu single atoms and particles supported on CeO2. This design enables controlled *CHO intermediate transformation through either hydrogenation with *H or coupling with *CO, leading to a highly selective CO2RR. Notably, our selective control strategy tunes the Faradaic efficiency from 61.1% for ethylene (C2H4) to 61.2% for methane (CH4). Additionally, the catalyst demonstrated a high current density and remarkable stability, exceeding 500 h of operation. This work not only provides efficient catalysts for selective CO2RR but also offers valuable insights into tailoring surface chemistry and designing catalysts for precise control over catalytic processes to achieve targeted product generation in CO2RR technology.

Experimental and DFT calculation study on the efficient removal of high fluoride wastewater from metallurgical wastewater by kaolinite

Fluoride pollution and water scarcity are urgent issues. Reducing fluoride concentration in water is crucial. Kaolinite has been used to study adsorption and fluoride removal in water and to characterize material properties. The experimental results showed that the adsorption capacity of kaolinite decreased with increasing pH. The highest adsorption of fluoride occurred at pH 2, with a capacity of 11.1 mg/g. The fluoride removal efficiency remained high after four regeneration cycles. The fitting results with the Freundlich isotherm model and the external diffusion model showed that the non-homogeneous adsorption of kaolinite fit the adsorption behavior better. Finally, the adsorption mechanism was analyzed by FT-IR and XPS. The binding energies of various adsorption sites and the chemical adsorption properties of atomic states were discussed in relation to DFT calculations. The results showed that Al and H sites were the main binding sites, and the bonding stability for different forms of fluoride varies, with the size of Al–F (−7.498 eV) > H–F (−6.04 eV) > H–HF (−3.439 eV) > Al–HF (−3.283 eV). Furthermore, the density of states and Mulliken charge distribution revealed that the 2p orbital of F was found to be active in the adsorption process and was the main orbital for charge transfer.

Pound–Drever–Hall feedforward: laser phase noise suppression beyond feedback

Pound–Drever–Hall (PDH) laser frequency stabilization is a powerful technique widely used for building narrow linewidth lasers. This technique is, however, ineffective in suppressing high-frequency (>100kHz) laser phase noise detrimental for many applications. Here, we introduce an effective method that can greatly enhance its high-frequency performance. The idea is to recycle the residual PDH signal of a laser locked to a cavity by feedforwarding it directly to the laser output field after a delay fiber. Using this straightforward method, we demonstrate a phase noise suppression capability about four orders of magnitude better than just using the usual PDH feedback for noise around a few MHz. We further find that this method exhibits noise suppression performance equivalent to cavity filtering. This method holds great promise for applications demanding highly stable lasers with diminished phase noise up to tens of MHz (e.g., precise and high-speed control of atomic and molecular quantum states).