Orbital Occupation Research Articles

Decoding the Role of eg Orbital Occupancy in Co Sites: Mechanistic Insights into Enhanced N2 Activation for Electrocatalytic Nitrate Synthesis

Decoding the Role of e<i>_g</i> Orbital Occupancy in Co Sites: Mechanistic Insights into Enhanced N₂ Activation for Electrocatalytic Nitrate Synthesis

Revisiting the global minimum of Au10 clusters.

This study employs high-level quantum chemical calculations to determine the global minimum structure of Au10 clusters definitively. Contrary to previous reports, coupled-cluster singles and doubles with perturbative triples [CCSD(T)] calculations with sizable quadruple-ζ basis sets incorporating the spin-orbit (SO) effect reveal that the planar 10.b structure is the true global minimum for Au10, not the three-dimensional 10.a structure. Two-component spin-orbit density functional theory calculations demonstrate that the SO effect is minimal for most Au10 isomers, except for the 10.f structure. A straightforward diagnostic tool is proposed for identifying Au cluster structures with strong spin-orbit coupling based on 6p orbital occupation. The calculated IR spectra based on Boltzmann averaging the six Au10 isomers show good agreement with recent experimental spectra although minor discrepancies are noted potentially due to interactions with Kr. The results suggest that the transition point to non-planar global minimum structures for Au clusters lies beyond Au10 but is nearby.

Ag Atom Induces Microstrain Environment around Cd Sites to Construct Diatomic Sites for Almost 100% CO2-to-CO Electroreduction.

Deeply understanding how local microstrain environment around diatomic sites influences their electronic state and adsorption is crucial for improving electrochemical CO2 reduction (eCO2R) reaction; however, precise engineering of the atomic microstrain environment is challenging. Herein, we fabricate Ag-CdTMT electrocatalysts with AgN2S2-CdN2S2 diatomic sites by anchoring Ag to the nodes of CdTMT (TMT = 2,4,6-trimercaptotriazine anion) coordination polymers. The Ag-CdTMT catalysts achieve approximately 100% Faradaic efficiency for CO reduction with an industrial level current density (∼200 mA cm-2 in H-cell). The embedded Ag atoms induce the formation of Ag-Cd diatomic sites with local microstrain, stretching Cd-N/S bonds, and reinforcing electron localization at Cd sites. The microstrain engineering and adjacent Ag atoms synergistically reduced Cd 4d-C 2p antibonding orbital occupancy for intensifying *COOH adsorption as the rate-determining step. This study provides novel insights into customizing the electronic structure of diatomic sites through strain engineering.

Intraplanar heterostructure-mediated activation of peroxydisulfate for singular-electron-transfer degradation of organic pollutants

Activating peroxydisulfate (PDS) through electron transfer pathways (ETP) is promising for degrading organic pollutants in aquatic environments. However, enhancing the activation selectivity remains a challenge. Herein, this study developed an intraplanar heterojunction with C-ring grafted g-C3N4 (CCN) as the catalyst, enabling PDS activation through a singular ETP. The CCN/PDS system achieved complete degradation and efficient mineralization (87.15 %) of bisphenol F (BPF), significantly reducing its ecological toxicity. Both experimental and theoretical investigations revealed that the intraplanar heterojunction could modulate the orbital occupation in g-C3N4/PDS, enhancing PDS adsorption and activation selectivity. Driven by the differences in the frontier orbital energy, the CCN/PDS system achieved a singular ETP without active species formation. The CCN/PDS system efficiently degraded BPF in complex water environments, showing performance stability across a wide pH range and against various coexisting ions. In a continuous-flow automatic catalytic device, the CCN/PDS system maintained a constant 100 % BPF degradation for 600 min. This study advances the understanding of PDS activation via singular ETP and introduces a new approach to water purification.

Large magnetocrystalline anisotropic energy and its impact on magnetostriction of L10-FePt

Abstract The origin of magnetocrystalline anisotropic energy (MAE) guided by spin–orbit coupling in the L10-FePt alloy was analyzed. Correlation of MAE with the calculated magnetoelastic constants in the single and polycrystal model was determined by means of first-principles calculations using density functional theory (DFT). More specifically, a systematic analysis of the large MAE and magnetostriction coefficients (λ’s) were done by means of post-processing of eigenvalues (orbital energies) and eigenfunctions (orbital occupancies). Our numerical analysis includes the convolution of the projected wave-function (density of states) of each orbital of the Fe and Pt sub-lattices into their orbital energies, which in principle should be valid for any solid regardless of the strength of the MAE. The determined anisotropic magnetostriction coefficients are of the λ ∼ 10 − 4 –10–3 order for several crystallographic directions; which is in accord to the known experimental data. However, the polycrystalline model based on the uniform stress approximation leads to a decrease of the λ by two orders in the overall magnetostrictive behavior ( λ ∼ 10 − 5 ). Such a large difference is not unexpected as the magnetostriction for polycrystalline FePt thin films were recorded as very low, thus validating the robustness of the current theoretical proposition of analyzing MAE.

Hydroxyl-Binding Induced Hydrogen Bond Network Connectivity on Ru-based Catalysts for Efficient Alkaline Hydrogen Oxidation Electrocatalysis.

Understanding the role of adsorbed intermediates at the polarized catalyst-electrolyte interface on the structure of electrical double layer (EDL) is essential for developing highly efficient electrocatalysts. Here, we prepared a series of unconventional face-centered-cubic (fcc) phase Ru-based catalysts (i.e. fcc-Ru, fcc-RuCr, and fcc-RuCrW) by rational tuning the binding energetics of hydroxyl intermediate to engineer the electrochemical interface and boost the performance of alkaline hydrogen oxidation reaction (HOR). The introduction of oxyphilic metals Cr and W can regulate the orbital occupation of Ru, promote the adsorption of hydroxyl species, resulting in an anomalous behavior that HOR performance under alkaline media exceeds acidic media. Experimental results and theoretical calculations unravel that the modulated adsorption of hydroxyl species on the electrode surface are responsible for the reconstruction of interfacial water structure and dynamic evolution of free water molecules from nearest to the electrode surface to above the gap region in the EDL, thereby leading to significantly increased water connectivity and hydrogen bond network. Our work reveals a new understanding of the surface intermediates in controlling the dynamic process of interfacial water and hydrogen bonding network in HOR electrocatalysis, and will guide rational design of advanced electrocatalysts through electrochemical interfacial engineering.

Hydroxyl‐Binding Induced Hydrogen Bond Network Connectivity on Ru‐based Catalysts for Efficient Alkaline Hydrogen Oxidation Electrocatalysis

Understanding the role of adsorbed intermediates at the polarized catalyst‐electrolyte interface on the structure of electrical double layer (EDL) is essential for developing highly efficient electrocatalysts. Here, we prepared a series of unconventional face‐centered‐cubic (fcc) phase Ru‐based catalysts (i.e. fcc‐Ru, fcc‐RuCr, and fcc‐RuCrW) by rational tuning the binding energetics of hydroxyl intermediate to engineer the electrochemical interface and boost the performance of alkaline hydrogen oxidation reaction (HOR). The introduction of oxyphilic metals Cr and W can regulate the orbital occupation of Ru, promote the adsorption of hydroxyl species, resulting in an anomalous behavior that HOR performance under alkaline media exceeds acidic media. Experimental results and theoretical calculations unravel that the modulated adsorption of hydroxyl species on the electrode surface are responsible for the reconstruction of interfacial water structure and dynamic evolution of free water molecules from nearest to the electrode surface to above the gap region in the EDL, thereby leading to significantly increased water connectivity and hydrogen bond network. Our work reveals a new understanding of the surface intermediates in controlling the dynamic process of interfacial water and hydrogen bonding network in HOR electrocatalysis, and will guide rational design of advanced electrocatalysts through electrochemical interfacial engineering.

Oxygen Vacancy-Mediated Synthesis of Inter-Atomically Ordered Ultrafine Pt-Alloy Nanoparticles for Enhanced Fuel Cell Performance.

Pt-based intermetallics are expected to be the highly active catalysts for oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells but still face great challenges in controllable synthesis of interatomically ordered and ultrafine intermetallic nanoparticles. Here, we propose an oxygen vacancy-mediated atomic diffusion strategy by mechanical alloying to reduce the energy barrier of the transition from interatomic disordering to ordering, and to resist interparticulate sintering via strong M-O-C bonding. This synthesis results in a nanosized core/shell structure featuring an interatomically ordered PtM core and a Pt shell of two to three atomic layers in thickness and can be extended to the multicomponent PtM (M = Co, FeCo, FeCoNi, FeCoNiGa) systems. The electron enrichment in the Pt outer shell induced by the compressive strain leads to the enhanced antibonding orbital occupation below the Fermi level and accelerated OH* desorption kinetics. The optimized PtCo-O/C-6 catalyst presents excellent ORR activity (mass activity = 1.28 A mgPt-1 at 0.9 ViR-free, peak power densities = 2.38/1.25 W cm-2 in H2-O2/-air) and durability (∼1% activity loss in over 50 h in air condition) in fuel cells at a total Pt loading of 0.1 mgPt cm-2. Furthermore, we establish a systematic correlation to elucidate the formation mechanisms of highly ordered intermetallic catalysts underlying oxygen vacancies. This study provides a general approach for the large-scale production of highly ordered and nanosized Pt-dispersed intermetallic catalysts.

Theoretical investigation of [formula omitted]-type doping modulated interlayer magnetic and potential topological phases transition in MnSb[formula omitted]Te[formula omitted] based systems

MnSb2Te4, as an important member of intrinsic magnetic topological insulator MnBi2Te4 family, shows promise for realizing quantum anomalous Hall effect (QAHE). However, interlayer A-type antiferromagnetic coupling has been a challenge to successfully observe this novel physical phenomenon in MnSb2Te4 system. Based on density functional theory, our calculations demonstrated that doping p-type non-magnetic elements into 2 SLs and 3 SLs of MnSb2Te4 can induce a magnetic phase transition from interlayer antiferromagnetic to ferromagnetic states with a Curie temperature up to 52.2 K. Moreover, our calculations present that interlayer ferromagnetic coupling and band gap in Ca-doped 2 SLs MnSb2Te4 systems can be further tuned by applying compressive strain. In addition, the interlayer ferromagnetic coupling in MnSb2Te4/Sb2Te3/MnSb2Te4 sandwich heterostructure by p-type doping can be enhanced, The detailed electronic structure analysis show that realization of interlayer ferromagnetic coupling is mainly related to a redistribution of d-electron orbital occupancy in Mn atoms of various SL layers. These findings not only advance the understanding of interlayer ferromagnetic order in ultrathin MnSb2Te4 layers, but also provide new way to realize the QAHE in MnSb2Te4 based systems without introducing extraneous magnetic disorder.

Bonding and Interactions in UO22+ for Ground and Core Excited States: Extracting Chemistry from Molecular Orbital Calculations.

Theoretical analyses of actinyls are necessary in order to understand and correctly interpret the chemical and physical properties of these molecules. Here, wave functions of Uranyl, UO22+, are considered for the ground state and for the core excited states where an electron is promoted from the U 3d5/2 shell into a low-lying unoccupied orbital that is U 5f antibonding with the ligand, O, orbitals. A focus is on the application of novel theoretical methods to the analysis of these wave functions so that measurements, especially with X-ray absorption, can be related to the UO22+ chemical bonding. The bond covalency is examined with these theoretical methods. The study includes how the covalent character is different for the ground and excited configurations and how this character changes as the U-O distance is changed. Furthermore, analyses are mode of how many-body effects may modify excitation energies and X-ray adsorption intensities. This includes determining the extent to which a single configuration provides a satisfactory model for the UO22+ wave functions. Two distinct types of many-body effects are considered. One involves the angular momentum coupling of the open shell electrons in the excited states to yield correct multiplets. The second adds excitations from shells that are bonding into the antibonding open shell space. These excitations are essential to properly describe the X-ray adsorption. While these many-body effects must be taken into account, their importance and their role can be explained and understood using orbitals and orbital occupations.

Tailoring the selective generation of high-valent cobalt-oxo by asymmetrically coordinated single-atom cobalt-activated peracetic acid for efficient water decontamination

The novel nonradical Fenton-like oxidation based on high-valent cobalt-oxo [CoIVO] species is a promising candidate for selectively removing emerging organic contaminants (EOCs) in complex water; however, efficient and targeted generation of CoIVO is hampered by the high Co-3d orbital occupancy and high bond dissociation energy of deprotonation. Herein, an O doping strategy to construct asymmetric coordination (CoN3O) in Co single-atom catalyst (Co-SAC) is developed to steer peracetic acid (PAA) activation for selectively generating CoIVO. Theoretical calculations suggest that asymmetric coordination of CoN3O could induce significant electron delocalization around Co centers, thus promote adsorption and peroxy O–O bond cleavage of PAA. The asymmetric electronic structure also exerts an additional local electric field, which favors the cleavage of O–H bond via a proton-coupled electron transfer pathway for subsequent CoIVO generation. Consistent with the theoretical prediction, the established CoN3O/PAA system exhibits admirable Fenton-like activity in degrading various EOCs to low-toxicity intermediates through exclusive generation of CoIVO, greatly reducing potential environmental risks. Our work provides a fundamental understanding of the structure–activity–selectivity relationships at an atomic level and provides a design guide to develop advanced CoIVO-involved Fenton-like catalyst for more extensive applications.

Enhanced Fenton-like reactions via interface electron reconstruction in low-crystallinity Fe[sbnd]Co bimetallic metal–organic frameworks: Bidirectional control of Fe (III) and Co (II) sites

In this study, the activity and stability of Fenton-like reactions are enhanced by constructing a low-crystallinity FeCo bimetallic metal–organic framework (FeCox-BDC (BDC denotes as terephthalic acid)) through interface electron reconstruction. However, the specific origins and mechanisms of their enhanced activity, particularly in Fenton-like reactions, remains unclear. Systematic analysis revealed that the isomorphic substitution of Co (II) reduces the coordination number and d-electron count at local Fe (III) sites, shifting the d-band centers (−1.59 eV) closer to the Fermi level. Additionally, Co 3d-orbitals can accept electrons, improving the occupation of antibonding orbitals. Notably, Fe (III) and Co (II) sites exhibit a synergistic effect: Fe (III) sites strongly adsorbed the Oα point of the peroxy bond (lOαOβ), while Co (II) sites efficiently activated Oβ. Within 5 min, FeCo1/3-BDC achieved a 98 % reduction in Rhodamine-B (RhB), surpassing Fe-BDC by a factor of 76 and homogeneous Fenton catalytic systems (Co (II)/peroxymonosulfate (PMS) and Fe (III)/Co (II)/PMS). This work provides a profound understanding of interface electron reconstruction, offering valuable insights into guiding Fenton-like mechanisms.

Electronic Structure Regulated Carbon-Based Single-Atom Catalysts for Highly Efficient and Stable Electrocatalysis.

Single-atom-catalysts (SACs) with atomically dispersed sites on carbon substrates have attained great advancements in electrocatalysis regarding maximum atomic utilization, unique chemical properties, and high catalytic performance. Precisely regulating the electronic structure of single-atom sites offers a rational strategy to optimize reaction processes associated with the activation of reactive intermediates with enhanced electrocatalytic activities of SACs. Although several approaches are proposed in terms of charge transfer, band structure, orbital occupancy, and the spin state, the principles for how electronic structure controls the intrinsic electrocatalytic activity of SACs have not been sufficiently investigated. Herein, strategies for regulating the electronic structure of carbon-based SACs are first summarized, including nonmetal heteroatom doping, coordination number regulating, defect engineering, strain designing, and dual-metal-sites scheming. Second, the impacts of electronic structure on the activation behaviors of reactive intermediates and the electrocatalytic activities of water splitting, oxygen reduction reaction, and CO2/N2 electroreduction reactions are thoroughly discussed. The electronic structure-performance relationships are meticulously understood by combining key characterization techniques with density functional theory (DFT)calculations. Finally, a conclusion of this paper and insights into the challenges and future prospects in this field are proposed. This review highlights the understanding of electronic structure-correlated electrocatalytic activity for SACs and guides their progress in electrochemical applications.

Orientation-dependent electronic structure in interfacial superconductors LaAlO3/KTaO3

Emergent superconductivity at the LaAlO3/KTaO3 interfaces exhibits a mysterious dependence on the KTaO3 crystallographic orientations. Here by soft X-ray angle-resolved photoemission spectroscopy, we directly resolve the electronic structure of the LaAlO3/KTaO3 interfacial superconductors and the non-superconducting counterpart. We find that the mobile electrons that contribute to the interfacial superconductivity show strong k⊥ dispersion. Comparing the superconducting and non-superconducting interfaces, the quasi-three-dimensional electron gas with over 5.5 nm spatial distribution ubiquitously exists and shows similar orbital occupations. The signature of electron-phonon coupling is observed and intriguingly dependent on the interfacial orientations. Remarkably, the stronger electron-phonon coupling signature correlates with the higher superconducting transition temperature. Our observations help scrutinize the theories on the orientation-dependent superconductivity and offer a plausible and straightforward explanation. The interfacial orientation effect that can modify the electron-phonon coupling strength over several nanometers sheds light on the applications of oxide interfaces in general.

Structure, Covalency, and Paramagnetism of Homoleptic Actinide and Lanthanide Amidinate Complexes.

Isostructural trivalent lanthanide and actinide amidinates bearing the N,N'-bis(isopropyl)benzamidinate (iPr2BA) ligand [LnIII/AnIII(iPr2BA)3] (Ln = La, Nd, Sm, Eu, Yb, Lu; An = U, Np) have been synthesized and characterized in both solid and solution states. All compounds were examined in the solid state utilizing single crystal X-ray diffraction (SC-XRD), revealing a notable deviation in the actinide series with shortened bond lengths compared to the trend in the lanthanide series, suggesting a nonionic contribution to the actinide-ligand bonding. Quantum-chemical bonding analysis further elucidated the nature of these interactions, highlighting increased covalency within the actinide series, as evidenced by higher delocalization indices and greater 5f orbital occupation, except for Th(III) and Pa(III), which demonstrated substantial 6d orbital occupancies. An in-depth paramagnetic NMR study in solution also sheds light on the covalent character of actinide-ligand bonding, with the separation of pseudocontact (PCS) and contact shift (FCS) contributions employing the Bleaney and Reilley method. This analysis unveiled significant contact contributions in the actinide complexes, indicating enhanced covalency in actinide-ligand bonding. To corroborate these observations, an accurate PCS calculation method based on the Kuprov equation, incorporating both the distribution of electronic spin density and magnetic susceptibility obtained from CASSCF calculations, was applied and compared with experimental values.

Symbolic transform optimized convolutional neural network model for high-performance prediction and analysis of MXenes hydrogen evolution reaction catalysts

Two-dimensional MXenes materials are expected to be cost-effective and efficient catalysts for hydrogen evolution reaction (HER) due to their tunable surface electronic structure. To optimize its catalytic activity, this study proposes a data-driven framework (CROSST) to generate descriptors through feature engineering and integrate them into a convolutional neural network to predict the HER performance of transition-metal (TM) anchored bis-transition-metal carbon-nitride (TM-M′2M′′CNO2) catalysts. The STCNN model achieves a coefficient of determination of more than 0.93, showing the ability to predict the Gibbs free energy of hydrogen adsorption (ΔGH) with high accuracy. We explored the microscopic mechanisms of HER activity through density functional theory and machine learning analysis. It was found that TM anchoring altered the charge distribution of the MXenes material, elevated the atomic orbital occupancy of neighboring O sites, and weakened the O adsorption of H, thus affecting the HER activity. These results provide a theoretical basis for the design of high-performance MXenes HER catalysts and contribute new research perspectives.

Tailoring electronic structure of stretchable freestanding single-crystal LaNiO3 thin film for enhanced oxygen evolution reaction

The comprehension of the electronic structure of an electrochemical catalyst, as a fundamental core content, has significantly accelerated advancements in competitive catalyst engineering since the adsorption and desorption abilities of an electrode are governed by its surface energy profile. However, achieving precise control over the electronic structure poses a significant challenge. Nanoporous materials, high-entropy systems, and layered double hydroxides frequently induce stoichiometric changes, leading to complexity such as electronic reconstruction, energy degeneracy disruption, and impurity energy levels. Here, we have successfully developed a stretchable freestanding single-crystal LaNiO3 thin film electrocatalyst enabling the accurate manipulation of the electronic structure on a large scale. Different from the rigid epitaxial heterostructure catalyst, we observed that with every 1 % increase in strain, the OER current of freestanding LaNiO3 is enhanced by ∼238 % compared to the pristine state. This is attributed to the dx2-y2 orbital occupation increasing by ∼7 %, and the eg-center decreasing by ∼0.05 eV, resulting in a weakened Ni-O adsorption.

First-principles study of electronic and magnetic properties of Fe atoms on Cu2N/Cu(100)

Abstract First-principles calculations were conducted to investigate the structural, electronic, and magnetic properties of single Fe atoms and Fe dimers on Cu2N/Cu(100). Upon adsorption of an Fe atom onto Cu2N/Cu(100), robust Fe–N bonds form, resulting in the incorporation of both single Fe atoms and Fe dimers within the surface Cu2N layer. The partial occupancy of Fe-3d orbitals lead to large spin moments on the Fe atoms. Interestingly, both single Fe atoms and Fe dimers exhibit in-plane magnetic anisotropy, with the magnetic anisotropy energy (MAE) of an Fe dimer exceeding twice that of a single Fe atom. This magnetic anisotropy can be attributed to the predominant contribution of the component along the x direction of the spin–orbital coupling Hamiltonian. Additionally, the formation of Fe–Cu dimers may further boost the magnetic anisotropy, as the energy levels of the Fe-3d orbitals are remarkably influenced by the presence of Cu atoms. Our study manifests the significance of uncovering the origin of magnetic anisotropy in engineering the magnetic properties of magnetic nanostructures.

Potential energy curves for F2, Cl2, and Br2 with the i-DMFT method.

The potential energy curves for dihalogens (F2, Cl2, and Br2) are calculated with the i-DMFT method proposed recently [Wang and Baerends, Phys. Rev. Lett. 128, 013001]. All electrons are correlated in a set of self-consistent-field eigenvalue equations, with the orbital occupation numbers obeying the Fermi-Dirac distribution. The only input is the dissociation energies of the molecules, which are usually available from an experimental database. The quality of the computed potential energy curve is examined by extracting spectroscopic parameters and rotation-vibration energy levels, which are compared with experiment data and other theoretical calculations.

Regulation of eg orbital occupancy in Ni-based metal-organic frameworks for efficient hydrogen peroxide electrosynthesis

Subject to the binding strength between the cathode and the oxo-intermediates, the hydrogen peroxide (H2O2) electrosynthesis with high productivity and high selectivity in oxygen reduction reaction (ORR) cannot be achieved simultaneously. In this work, the dual-metal-organic frameworks (NiFe-MOFs) is designed and synthesized, in which the eg orbital occupancy of Ni nodes is regulated by the super-exchange effect of Ni(2+σ)+-O-Fe(3-σ)+ bond. As a result, the binding strength between the cathode and the oxo-intermediates (*O2, *OOH) is optimized, which efficiently promotes oxygen reduction kinetics and inhibits O-O bond breakage. The H2O2 yield of NiFe-MOFs cathode reaches 1.83 mol·g−1·h−1 with a Faraday efficiency of 96.3 % at 0.5 V vs. RHE, which is far superior to Ni-MOFs (0.21 mol·g−1·h−1, 65.4 %), Fe-MOFs (0.65 mol·g−1·h−1, 57.5 %). This work offers a new strategy to design and develop cathodic catalysts for H2O2 electrosynthesis with high productivity and high selectivity.