XB2Bi2 (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons.

Planar tetracoordinate silicon, germanium, tin, and lead (ptSi/Ge/Sn/Pb) species are scarce and exotic. Here, we report a series of penta-atomic ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters with 20 valence electrons (VEs). Ternary XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess beautiful fan-shaped structures, with a Bi-B-B-Bi chain surrounding the central X core. The unbiased density functional theory (DFT) searches and high-level CCSD(T) calculations reveal that these ptSi/Ge/Sn/Pb species are the global minima on their potential energy surfaces. Born-Oppenheimer molecular dynamics (BOMD) simulations indicate that XB2Bi2 (X = Si, Ge, Sn, Pb) clusters are robust. Bonding analyses indicate that 20 VEs are perfect for the ptX XB2Bi2 (X = Si, Ge, Sn, Pb): two lone pairs of Bi atoms; one 5c-2e π, and three σ bonds (two Bi-X 2c-2e and one B-X-B 3c-2e bonds) between the ligands and X atom; three 2c-2e σ bonds and one delocalized 4c-2e π bond between the ligands. The ptSi/Ge/Sn/Pb XB2Bi2 (X = Si, Ge, Sn, Pb) clusters possess 2π/2σ double aromaticity, according to the (4n + 2) Hückel rule.

Controlling the Valence-Electron Arrangement of Nickel Active Centers for Efficient Hydrogen Oxidation Electrocatalysis.

The valence-electron arrangement of heterogeneous catalysts can significantly affect the binding behavior of absorbates. However, it remains a challenge to understand the role of the valence-electron arrangement in electrocatalysis, which limits its utilization as a tool to design efficient electrocatalysts. Here, we describe experiments in which the valence-electron arrangement of Ni active centers for hydrogen oxidation is controlled precisely by using Ni-vacancy-enriched Ni3 N as a platform. These Ni vacancies can promote the valence-electron delocalization of OH-adsorption centers to enhance the Ni ds-O 2p valence-electron-orbital interaction with elevated OH adsorption. Meanwhile, the deficit of valence-electrons of H-adsorption centers at Ni vacancies can lower Ni ds-H 1s interaction with weakened H binding. Relative to Ni3 N poor in vacancies, the Ni-vacancy-enriched Ni3 N showed a mass activity enhanced by 15-fold. This strategy paves a rational way to design efficient catalysts by finely tuning the valence-electron arrangement.

Reactivity and Lability Modulated by a Valence Electron Moving in and out of 25-Atom Gold Nanoclusters.

The emergence of atomically precise metal nanoclusters with unique electronic structures provides access to currently inaccessible catalytic challenges at the single-electron level. We investigate the catalytic behavior of gold Au25 (SR)18 nanoclusters by monitoring an incoming and outgoing free valence electron of Au 6s1 . Distinct performances are revealed: Au25 (SR)18 - is generated upon donation of an electron to neutral Au25 (SR)18 0 and this is associated with a loss in reactivity, whereas Au25 (SR)18 + is generated from dislodgment of an electron from neutral Au25 (SR)18 0 with a loss in stability. The reactivity diversity of the three Au25 (SR)18 clusters stems from different affinities with reactants and the extent of intramolecular charge migration during the reactions, which are closely associated with the valence occupancies of the clusters varied by one electron. The stability difference in the three clusters is attributed to their different equilibria, which are established between the AuSR dissociation and polymerization influenced by one electron.

Dimensionality and Valency Dependent Quantum Growth of Metallic Nanostructures: A Unified Perspective.

Quantum growth refers to the phenomena in which the quantum mechanically confined motion of electrons in metallic wires, islands, and films determines their overall structural stability as well as their physical and chemical properties. Yet to date, there has been a lack of a unified understanding of quantum growth with respect to the dimensionality of the nanostructures as well as the valency of the constituent atoms. Based on a first-principles approach, we investigate the stability of nanowires, nanoislands, and ultrathin films of prototypical metal elements. We reveal that the Friedel oscillations generated at the edges (or surfaces) of the nanostructures cause corresponding oscillatory behaviors in their stability, leading to the existence of highly preferred lengths (or thicknesses). Such magic lengths of the nanowires are further found to depend on both the number of valence electrons and the radial size, with the oscillation period monotonously increasing for alkali and group IB metals, and monotonously decreasing for transition and group IIIA-VA metals. When the radial size of the nanowires increases to reach ∼10 Å, the systems equivalently become nanosize islands, and the oscillation period saturates to that of the corresponding ultrathin films. These findings offer a generic perspective of quantum growth of different classes of metallic nanostructures.

Pentaatomic planar tetracoordinate silicon with 14 valence electrons: a large-scale global search of SiX(n)Y(m)(q) (n + m = 4; q = 0, ±1, -2; X, Y = main group elements from H to Br).

Designing and characterizing the compounds with exotic structures and bonding that seemingly contrast the traditional chemical rules are a never-ending goal. Although the silicon chemistry is dominated by the tetrahedral picture, many examples with the planar tetracoordinate-Si skeletons have been discovered, among which simple species usually contain the 17/18 valence electrons. In this work, we report hitherto the most extensive structural search for the pentaatomic ptSi with 14 valence electrons, that is, SiXnYm(q) (n + m = 4; q = 0, ±1, -2; X, Y = main group elements from H to Br). For 129 studied systems, 50 systems have the ptSi structure as the local minimum. Promisingly, nine systems, that is, Li3SiAs(2-), HSiY3 (Y = Al/Ga), Ca3SiAl(-), Mg4Si(2-), C2LiSi, Si3Y2 (Y = Li/Na/K), each have the global minimum ptSi. The former six systems represent the first prediction. Interestingly, in HSiY3 (Y = Al/Ga), the H-atom is only bonded to the ptSi-center via a localized 2c-2e σ bond. This sharply contradicts the known pentaatomic planar-centered systems, in which the ligands are actively involved in the ligand-ligand bonding besides being bonded to the planar center. Therefore, we proposed here that to generalize the 14e-ptSi, two strategies can be applied as (1) introducing the alkaline/alkaline-earth elements and (2) breaking the peripheral bonding. In light of the very limited global ptSi examples, the presently designed six systems with 14e are expected to enrich the exotic ptSi chemistry and welcome future laboratory confirmation.

Modulating Valence Electrons and Na Occupancy in Layered Cathodes for High-Performance Na-Ion Batteries.

Na-ion batteries (NIBs) hold promise as a leading option for large-scale energy storage. However, their development faces challenges due to the lack of high-performance cathode materials. P2-type layered oxides are seen as potential cathode materials for NIBs due to higher structure stability, yet their commercialization is hindered by limited capacity and subpar phase transitions during Na extraction and insertion at high voltages. In this study, we introduce a new P2-type cathode material, Na0.76Ni0.23Li0.1Ti0.02Mn0.65O1.998F0.02 (NLTMOF), synthesized with ternary Li/Ti/F substitution. This modification of ternary Li/Ti/F substitution significantly tailors the electronic structures, increasing the number of valence electrons near the Fermi energy level. This facilitates the electronic conductivity and their involvement in charge compensation, thereby enhancing reversible capacity. Additionally, ternary doping synergistically adjusts the Na occupancy at the Na layer for favorable Na extraction without P2-O2 phase transitions even under a high voltage of 4.4 V, boosting cycling stability. As a result, NLTMOF demonstrates a reversible capacity of 110.0 and 132.2 mAh g-1 at 2-4.2 and 2-4.4 V, respectively, and maintains greatly enhanced cycling stability over long cycles. This study sheds light on the design of transition metal oxides for advanced cathode materials through the modulation of electronic structure and Na occupancy in cathode materials, thus promoting the development of NIBs.

Mapping valence electron distributions with multipole density formalism using 4D-STEM.

Recent advancement in aberration correction and detector technology opened a door to various applications using 4D-STEM, which yields a diffraction pattern for each scanning position within a crystal unit-cell in scanning transmission electron microscopy (STEM) and generates incredible amounts of data in momentum space. Currently 4D-STEM analysis relies on the center-of-mass of the diffraction patterns in electric field and charge density mapping. It only derives the total projected charge density and is limited to phase objects, e.g. extremely thin samples. Here, we propose a new analytical method to accurately map aspherical valence electron distributions with atom-centered multipolar functions formalism using the whole 4D-STEM dataset. We demonstrate that, with the full dynamical calculations for various sample thicknesses, the method is sensitive not only to the miniscule charge transfer, but also to the atomic site symmetry and aspherical electron orbitals. The process of the refinement is much more robust and reliable than quantitative convergent beam electron diffraction.

Valence electron energy-loss spectroscopy study of ZrSiO4 and ZrO2.

ZrSiO4 (zircon) and m-ZrO2 (zirconia) are fundamental and industrially important materials. This work reports the detailed valence electron energy-loss spectroscopy (VEELS) studies of these compounds. The dielectric response functions, as well as single-electron interband transition spectra, are derived from VEELS data for both ZrSiO4 and m-ZrO2, in the range 5-50 eV using the Kramers-Kronig analysis method. Our interpretation of the interband transitions is given with the aid of ab initio calculations of density of states. The bandgap energies for both materials are also measured using VEELS. The surface and bulk plasmons are identified: the surface plasmon peaks locate at around 12 eV, and two bulk plasmon peaks are ∼15-16 eV and ∼25-27 eV, respectively. Although similarities in the VEELS exist between ZrSiO4 and m-ZrO2, two major differences are also noticed and explained in terms of composition and structure differences.