Search Results (20)

Constructing two-dimensional (2D) novel materials using superatoms as building blocks is currently a highly promising research field. In this study, by employing an oxidation strategy and based on first-principles calculations, we successfully predicted two types of 2D borides, namely B₁₂X₂H₆ (X=O, S), with icosahedral B₁₂ serving as their core structural unit. Ab initio molecular dynamics simulations demonstrated that these two borides exhibit exceptionally high structural stability, retaining their original structural characteristics even under extreme temperature conditions as high as 2200 K. Electronic structure calculations revealed that B₁₂O₂H₆ and B₁₂S₂H₆ are both wide-bandgap indirect semiconductors, with bandgap widths reaching 4.92 eV and 5.25 eV, respectively. Analysis via deformation potential theory showed that the phonon-limited carrier mobilities of B₁₂X₂H₆ can reach up to 1469 cm²V⁻¹s⁻¹ (for B₁₂O₂H₆) and 635 cm²V⁻¹s⁻¹ (for B₁₂S₂H₆). Notably, the surfaces of B₁₂X₂H₆ demonstrate excellent migration performance for alkali metal ions, with migration barriers as low as 0.15 eV (for B₁₂O₂H₆) and 0.033 eV (for B₁₂S₂H₆). This study not only expands the family of 2D materials based on B₁₂ superatoms but also provides a solid theoretical foundation for the potential application of B₁₂X₂H₆ in the field of low-dimensional materials. Full article

Si-based photonics has garnered considerable attention as a future device for complementary metal–oxide–semiconductor (CMOS) computing. However, few studies have investigated Si-based light sources highly compatible with Si ultra large-scale integration processing. In this study, we observed stable light emission at room temperature from superatom-like β–FeSi₂–core/Si–shell quantum dots (QDs). The β–FeSi₂–core/Si–shell QDs, with an areal density as high as ~10¹¹ cm⁻² were fabricated by self-aligned silicide process of Fe–silicide capped Si–QDs on ~3.0 nm SiO₂/n–Si (100) substrates, followed by SiH₄ exposure at 400 °C. From the room temperature photoluminescence characteristics, β–FeSi₂ core/Si–shell QDs can be regarded as active elements in optical applications because they offer the advantages of photonic signal processing capabilities and can be combined with electronic logic control and data storage. Full article

We investigate steady-state entanglement in a hybrid optomechanical cavity coupled to a Rydberg atomic ensemble confined within a single blockade region. The ensemble behaves as one superatom due to the rigid dipole blockade effect. Through optomechanical coupling, three types of bipartite entanglement emerge among the cavity, the Rydberg superatom, and the movable mirror. As the principal quantum number of the Rydberg atoms increases (leading to reduced atomic decay rates), the direct cavity–mirror coupling entanglement is redistributed into direct cavity–superatom coupling entanglement and indirect superatom–mirror coupling entanglement. Counterintuitively, this redistribution culminates in the complete suppression of two direct coupling entanglements, leaving only the indirect coupling entanglement persistent under resonant Stokes sideband conditions. Systematic parameter tuning reveals entanglement transfer pathways and establishes the preference of the superatom–mirror entanglement for specific principal quantum numbers. Furthermore, we demonstrate the thermal robustness of the surviving entanglement up to experimentally accessible temperatures. These findings advance the understanding of quantum entanglement in hybrid quantum systems and suggest applications in quantum information processing. Full article

The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at the atomic level in the production of clusters, including the quantity of dopant, characteristic of ligands, charge state of precursors, and structural transformation, have remained a challenge. Herein, we report the synthesis, purification, and characterization of a new bimetallic hydride cluster, [AuCu₁₁(H){S₂P(OⁱPr)₂}₆(C≡CPh)₃] (AuCu₁₁H). The hydride position in AuCu₁₁H was determined using DFT calculations. AuCu₁₁H comprises a ligand-stabilized defective fcc Au@Cu₁₁ cuboctahedron. AuCu₁₁H is metastable and undergoes a spontaneous transformation through ligand exchange into the isostructural [AuCu₁₁(Cl){S₂P(OⁱPr)₂}₆(C≡CPh)₃] (AuCu₁₁Cl) and into the complete cuboctahedral [AuCu₁₂{S₂P(OⁱPr)₂}₆(C≡CPh)₄]⁺ (AuCu₁₂) through an increase in nuclearity. These structural transformations were tracked by NMR and mass spectrometry. Full article

Copper homometallic and copper-rich heterometallic nanoclusters with some Cu(0) character are reviewed. Their structure and stability are discussed in terms of their number of “free” electrons. In many aspects, this structural chemistry differs from that of their silver or copper homologs. Whereas the two-electron species are by far the most numerous, only one eight-electron species is known, but more electron-rich nanoclusters have also been reported. Owing to the relatively recent development of this chemistry, it is likely that more electron-rich species will be reported in the future. Full article

A superatom is a cluster of atoms that acts like a single atom. Two main groups of superatoms are superalkalis and superhalogens, which mimic the chemistry of alkali and halogen atoms, respectively. The ionization energies of superalkalis are smaller than those of alkalis (<3.89 eV for cesium atom), and the electron affinities of superhalogens are larger than that of halogens (>3.61 eV for chlorine atom). Exploring new superalkali/superhalogen aims to provide reliable data and predictions of the use of such compounds as redox agents in the reduction/oxidation of counterpart systems, as well as the role they can play more generally in materials science. The low ionization energies of superalkalis make them candidates for catalysts for CO₂ conversion into renewable fuels and value-added chemicals. The large electron affinity of superhalogens makes them strong oxidizing agents for bonding and removing toxic molecules from the environment. By using the superatoms as building blocks of cluster-assembled materials, we can achieve the functional features of atom-based materials (like conductivity or catalytic potential) while having more flexibility to achieve higher performance. This feature paper covers the issues of designing such compounds and demonstrates how modifications of the superatoms (superhalogens and superalkalis) allow for the tuning of the electronic structure and might be used to create unique functional materials. The designed superatoms can form stable perovskites for solar cells, electrolytes for Li-ion batteries of electric vehicles, superatomic solids, and semiconducting materials. The designed superatoms and their redox potential evaluation could help experimentalists create new materials for use in fields such as energy storage and climate change. Full article

The superatomic structure of film-forming sols obtained by the acid hydrolysis of tetraethoxysilane (TEOS) in an aqueous medium (free of organic solvents) was studied using the SAXS method. The formation of nanoparticles (NPs) was confirmed in alcohol-free silica sols with both a low (1 vol. %) content of TEOS and a high (10 vol. %) content of TEOS, hydrolyzed in an aqueous-alcoholic medium. A trimodal size distribution was revealed for the resulting NPs, with radii ranging from less than 1 nm to ~11 nm. The volume fraction of NPs tends to grow with increases in TEOS concentration, as well as with the introduction of magnetic NPs of iron oxides into silica sols. The synthesized silica sols and suspensions based on silica sols with Fe_xO_y NPs were used for the pre-sowing treatment of white and cauliflower cabbage seeds in order to provide a functional coating on their surfaces, thereby improving seed germination, stimulating their growth in the early stages of development, and suppressing the effect of phytopathogens. The effect of the pre-sowing seed treatment in sol-gel compositions on seed germination and the growth characteristics of plant seedlings is analyzed, including the influence of iron-oxide magnetic NPs’ compositions and concentrations in silica sols. Full article

Spherical nanoclusters with countable member atoms and delocalized valence orbitals are superatoms with properties analogous to those of simple atoms. This is reflected, in particular, in their optical spectra and magnetic properties, in a similar sense to transition metal ions and complexes. Clusters can be of low-spin or high-spin with considerable contributions to magnetism by the large cluster orbital magnetic moment. Due to the large radius of the clusters, they can be diamagnetic with an unusually high diamagnetic susceptibility. Gold and platinum, which in the bulk are non-magnetic, show pronounced superparamagnetism associated with their high-spin nature, and the magnetic moment can be trapped in symmetry-breaking environments so that hysteresis pertains far beyond room temperature. A significant deviation from hydrogen-like orbitals results from the shape of the confining potential, which has the effect that the orbital quantum number ℓ is not limited to values less than the principal quantum number n. Full article

Transition-metal-doped clusters have long been attracting great attention due to their unique geometries and interesting physical and/or chemical properties. In this paper, the geometries of the lowest- and lower-energy CoK_n (n = 2–12) clusters have been screened out using particle swarm optimization and first principles relaxation. The results show that except for CoK₂ the other CoK_n (n = 3–12) clusters are all three-dimensional structures, and CoK₇ is the transition structure from which the lowest energy structures are cobalt atom-centered cage-like structures. The stability, the electronic structures, and the magnetic properties of CoK_n clusters (n = 2–12) clusters are further investigated using the first principles method. The results show that the medium-sized clusters whose geometries are cage-like structures are more stable than smaller-sized clusters. The electronic configuration of CoK_n clusters could be described as 1S1P1D according to the spherical jellium model. The main components of petal-shaped D molecular orbitals are Co-d and K-s states or Co-d and Co-s states, and the main components of sphere-like S molecular orbitals or spindle-like P molecular orbitals are K-s states or Co-s states. Co atoms give the main contribution to the total magnetic moments, and K atoms can either enhance or attenuate the total magnetic moments. CoK_n (n = 5–8) clusters have relatively large magnetic moments, which has a relation to the strong Co-K bond and the large amount of charge transfer. CoK₄ could be a magnetic superatom with a large magnetic moment of 5 μ_B. Full article

We have demonstrated the high–density formation of super–atom–like Si quantum dots with Ge–core on ultrathin SiO₂ with control of high–selective chemical–vapor deposition and applied them to an active layer of light–emitting diodes (LEDs). Through luminescence measurements, we have reported characteristics carrier confinement and recombination properties in the Ge–core, reflecting the type II energy band discontinuity between the Si–clad and Ge–core. Additionally, under forward bias conditions over a threshold bias for LEDs, electroluminescence becomes observable at room temperature in the near–infrared region and is attributed to radiative recombination between quantized states in the Ge–core with a deep potential well for holes caused by electron/hole simultaneous injection from the gate and substrate, respectively. The results will lead to the development of Si–based light–emitting devices that are highly compatible with Si–ultra–large–scale integration processing, which has been believed to have extreme difficulty in realizing silicon photonics. Full article

Doping alkali metals into boron clusters can effectively compensate for the intrinsic electron deficiency of boron and lead to interesting boron-based binary clusters, owing to the small electronegativity of the former elements. We report on the computational design of a three-layered sandwich cluster, Na₅B₇, on the basis of global-minimum (GM) searches and electronic structure calculations. It is shown that the Na₅B₇ cluster can be described as a charge-transfer complex: [Na₄]²⁺[B₇]³⁻[Na]⁺. In this sandwich cluster, the [B₇]³⁻ core assumes a molecular wheel in shape and features in-plane hexagonal coordination. The magic 6π/6σ double aromaticity underlies the stability of the [B₇]³⁻ molecular wheel, following the (4n + 2) Hückel rule. The tetrahedral Na₄ ligand in the sandwich has a [Na₄]²⁺ charge-state, which is the simplest example of three-dimensional aromaticity, spherical aromaticity, or superatom. Its 2σ electron counting renders σ aromaticity for the ligand. Overall, the sandwich cluster has three-fold 6π/6σ/2σ aromaticity. Molecular dynamics simulation shows that the sandwich cluster is dynamically fluxional even at room temperature, with a negligible energy barrier for intramolecular twisting between the B₇ wheel and the Na₄ ligand. The Na₅B₇ cluster offers a new example for dynamic structural fluxionality in molecular systems. Full article

A two-dimensional graphene-like carbon nitride (g-CN) monolayer decorated with the superatomic cluster NLi₄ was studied for reversible hydrogen storage by first-principles calculations. Molecular dynamics simulations show that the g-CN monolayer has good thermal stability at room temperature. The NLi₄ is firmly anchored on the g-CN monolayer with a binding energy of −6.35 eV. Electronic charges are transferred from the Li atoms of NLi₄ to the g-CN monolayer, mainly due to the hybridization of Li(2s), C(2p), and N(2p) orbitals. Consequently, a spatial local electrostatic field is formed around NLi₄, leading to polarization of the adsorbed hydrogen molecules and further enhancing the electrostatic interactions between the Li atoms and hydrogen. Each NLi₄ can adsorb nine hydrogen molecules with average adsorption energies between −0.152 eV/H₂ and −0.237 eV/H₂. This range is within the reversible hydrogen storage energy window. Moreover, the highest achieved gravimetric capacity is up to 9.2 wt%, which is superior to the 5.5 wt% target set by the U.S. Department of Energy. This study shows that g-CN monolayers decorated with NLi₄ are a good candidate for reversible hydrogen storage. Full article

Superatoms are promising materials for their potential in elemental substitution and as new building blocks. Thus far, various synthesis methods of thiol-protected Au clusters including an Au₂₅ superatom have been investigated. However, previously reported methods were mainly depending on the thermodynamic stability of the aimed clusters. In this report, a synthesis method for thiol-protected Au clusters using a dendrimers template is proposed. In this method, the number of Au atoms was controlled by the stepwise complexation feature of a phenylazomethine dendrimer. Therefore, synthesis speed was increased compared with the case without the dendrimer template. Hybridization for the Au₂₅ superatoms was also achieved using the complexation control of metals. Full article

A superatom is a cluster composed of a specific number of atoms. We recently found that the superatom-like X@Ga₁₂ (X = Li~Kr) clusters has the periodic energy levels of the specific orbitals 2S and 2P by means of the DV-Xα molecular orbital calculation method. This periodicity in energy levels has not been seen in 1D or 1F orbitals. We supposed that the periodicity of the energy levels of the 2S and 2P superatomic-like orbitals come from the same symmetry between atomic orbitals as the central atom X and the surrounding specific orbitals, according to the Jellium model. Both the s and p atomic orbitals of the central atom X in the superatom-like X@Ga₁₂ have a large shielding effect, suggesting that the s and p atomic orbitals interact strongly with both 2S and 2P superatomic-like orbitals. The energy level periodicity has the potential to periodically change the number of electrons located in the 1D and 1F orbitals, which is related to magnetic properties and is expected to be useful for novel magnetic devices by periodically controlling the magnetism of superatoms. Full article

Based on the dipole blockade effect and with the aid of the superatom (SA) model, we propose a scheme to investigate the correlated evolution of two Rydberg sub-superatoms (SSAs), formed by two spatially separated atomic Rydberg sub-ensembles but in the same blockade region. Starting from the pure separable states, we investigate the in-phase or anti-phase correlated dynamics and explore how two Rydberg SSAs entangle with each other mediated by a single Rydberg excitation. Starting from the entangled states, we discuss the robustness of the system against decoherence induced by the dephasing rate. Our results show that both the correlated evolution of two Rydberg SSAs and their collective-state entanglement are usually sensitive to the number of each Rydberg SSA. This allows us to coherently manipulate the Rydberg ensemble over long distances from the single-quantum level to the mesoscopic level by changing the number of atoms. Furthermore, the method for dividing an SA into two SSAs and obtaining their spin operators without any approximation can be readily generalized to the case of many SSAs. It may have potential promising applications in quantum information processing and provide an attractive platform to study the quantum-classical correspondence, many-body physics and so on. Full article