Probing the Structural and Electronic Properties of the Anionic and Neutral Tellurium-Doped Boron Clusters TeBnq (n = 3-16, q = 0, -1).

In this study, we employ density functional theory along with the artificial bee colony algorithm for cluster global optimization to explore the low-lying structures of TeBnq (n = 3-16, q = 0, -1). The primary focus is on reporting the structural properties of these clusters. The results reveal a consistent doping pattern of the tellurium atom onto the in-plane edges of planar or quasi-planar boron clusters in the most energetically stable isomers. Additionally, we simulate the photoelectron spectra of the cluster anions. Through relative stability analysis, we identify three clusters with magic numbers -TeB7-, TeB10, and TeB12. The aromaticity of these clusters is elucidated using adaptive natural density partitioning (AdNDP) and magnetic properties analysis. Notably, TeB7- exhibits a perfect σ-π doubly aromatic structure, while TeB12 demonstrates strong island aromaticity. These findings significantly contribute to our understanding of the structural and electronic properties of these clusters.

Exploring the Structural and Electronic Properties of Niobium Carbide Clusters: A Density Functional Theory Study.

This paper systematically investigates the structure, stability, and electronic properties of niobium carbide clusters, NbmCn (m = 5, 6; n = 1-7), using density functional theory. Nb5C2 and Nb5C6 possess higher dissociation energies and second-order difference energies, indicating that they have higher thermodynamic stability. Moreover, ab initio molecular dynamics (AIMD) simulations are used to demonstrate the thermal stability of these structures. The analysis of the density of states indicates that the molecular orbitals of NbmCn (m = 5, 6; n = 1-7) are primarily contributed by niobium atoms, with carbon atoms having a smaller contribution. The composition of the frontier molecular orbitals reveals that niobium atoms contribute approximately 73.1% to 99.8% to NbmCn clusters, while carbon atoms contribute about 0.2% to 26.9%.

Investigation of Structures, Stabilities, and Electronic and Magnetic Properties of Niobium Carbon Clusters Nb7Cn (n = 1-7).

The geometrical structures, relative stabilities, and electronic and magnetic properties of niobium carbon clusters, Nb7Cn (n = 1-7), are investigated in this study. Density functional theory (DFT) calculations, coupled with the Saunders Kick global search, are conducted to explore the structural properties of Nb7Cn (n = 1-7). The results regarding the average binding energy, second-order difference energy, dissociation energy, HOMO-LUMO gap, and chemical hardness highlight the robust stability of Nb7C3. Analysis of the density of states suggests that the molecular orbitals of Nb7Cn primarily consist of orbitals from the transition metal Nb, with minimal involvement of C atoms. Spin density and natural population analysis reveal that the total magnetic moment of Nb7Cn predominantly resides on the Nb atoms. The contribution of Nb atoms to the total magnetic moment stems mainly from the 4d orbital, followed by the 5p, 5s, and 6s orbitals.

Exploring the stability and aromaticity of rare earth doped tin cluster MSn16- (M = Sc, Y, La).

Rare earth elements have high chemical reactivity, and doping them into semiconductor clusters can induce novel physicochemical properties. The study of the physicochemical mechanisms of interactions between rare earth and tin atoms will enhance our understanding of rare earth functional materials from a microscopic perspective. Hence, the structure, electronic characteristics, stability, and aromaticity of endohedral cages MSn16- (M = Sc, Y, La) have been investigated using a combination of the hybrid PBE0 functional, stochastic kicking, and artificial bee colony global search technology. By comparing the simulated results with experimental photoelectron spectra, it is determined that the most stable structure of these clusters is the Frank-Kasper polyhedron. The doping of atoms has a minimal influence on density of states of the pure tin system, except for causing a widening of the energy gap. Various methods such as ab initio molecular dynamics simulations, the spherical jellium model, adaptive natural density partitioning, localized orbital locator, and electron density difference are employed to analyze the stability of these clusters. The aromaticity of the clusters is examined using iso-chemical shielding surfaces and the gauge-including magnetically induced currents. This study demonstrates that the stability and aromaticity of a tin cage can be systematically adjusted through doping.

Aromatic and magnetic properties in a series of heavy rare earth-doped Ge6 cluster anions.

A series of pentagonal bipyramidal anionic germanium clusters doped with heavy rare earth elements, REGe 6 - (RE = Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu), have been identified at the PBE0/def2-TZVP level using density functional theory (DFT). Our findings reveal that the centrally doped pentagonal ring structure demonstrates enhanced stability and heightened aromaticity due to its uniform bonding characteristics and a larger charge transfer region. Through natural population analysis and spin density diagrams, we observed a monotonic decrease in the magnetic moment from Gd to Yb. This is attributed to the decreasing number of unpaired electrons in the 4f orbitals of the heavy rare earth atoms. Interestingly, the system doped with Er atoms showed lower stability and anti-aromaticity, likely due to the involvement of the 4f orbitals in bonding. Conversely, the systems doped with Gd and Tb atoms stood out for their high magnetism and stability, making them potential building blocks for rare earth-doped semiconductor materials.

Making Sense of the Growth Behavior of Ultra-High Magnetic Gd2-Doped Silicon Clusters.

The growth behavior, stability, electronic and magnetic properties of the Gd2Sin- (n = 3-12) clusters are reported, which are investigated using density functional theory calculations combined with the Saunders 'Kick' and the Artificial Bee Colony algorithm. The lowest-lying structures of Gd2Sin- (n = 3-12) are all exohedral structures with two Gd atoms face-capping the Sin frameworks. Results show that the pentagonal bipyramid (PB) shape is the basic framework for the nascent growth process of the present clusters, and forming the PB structure begins with n = 5. The Gd2Si5- is the potential magic cluster due to significantly higher average binding energies and second order difference energies, which can also be further verified by localized orbital locator and adaptive natural density partitioning methods. Moreover, the localized f-electron can be observed by natural atomic orbital analysis, implying that these electrons are not affected by the pure silicon atoms and scarcely participate in bonding. Hence, the implantation of these elements into a silicon substrate could present a potential alternative strategy for designing and synthesizing rare earth magnetic silicon-based materials.

A joint experimental and theoretical study on structural, electronic, and magnetic properties of MnGen - (n = 3-14) clusters.

A systematic structure and property investigation of MnGen - (n = 3-14) was conducted by means of density functional theory coupled with mass-selected anion photoelectron spectroscopy. This combined theoretical and experimental study allows global minimum and coexistence structures to be identified. It is found that the pentagonal bipyramid shape is the basic framework for the nascent growth process of MnGen - (n = 3-10), and from n = 10, the endohedral structures can be found. For n = 12, the anion MnGe12 - cluster probably includes two isomers: a major isomer with a puckered hexagonal prism geometry and a minor isomer with a distorted icosahedron geometry. Specifically, the puckered hexagonal prism isomer follows the Wade-Mingos rules and can be suggested as a new kind of superatom with the magnetic property. Furthermore, the results of adaptive natural density partitioning and deformation density analyses suggest a polar covalent interaction between Ge and Mn for endohedral clusters of MnGe12 -. The spin density and natural population analysis indicate that MnGen - clusters have high magnetic moments localized on Mn. The density of states diagram visually shows the significant spin polarization for endohedral structures and reveals the weak interaction between the Ge 4p orbital and the 4s, 3d orbitals of Mn.

Microsolvation of Co- in water: Density functional theory calculations coupled with stochastic kicking method.

The hydrated clusters [Formula: see text] (n = 1-4) in gas phase are studied by density functional theory calculations (DFT) coupled with stochastic kicking method. The global minimum structure of [Formula: see text] exhibits low-symmetry pattern since only one H atom of water molecules interact with Co- ion and other ones associate with a network of hydrogen bonds. The Co- ion prefers to locate at vertex site of the water molecular clusters in such way to reduce the repulsion with O atom. These results elucidate the formation of these low-lying isomers are determined by the delicate balance between ion-water and water-water interactions.

Probing the structural, electronic, and adsorptive properties of Au16O2- clusters.

Great progress has been made in O2 adsorption on gold clusters. However, systematic investigations of O2 adsorption on [Formula: see text] clusters have not been reported. Here, we present a systematic study of the structural, electronic, and adsorptive properties of [Formula: see text] clusters by density functional theory (DFT) calculations coupled with stochastic kicking method. Global minimum searches for [Formula: see text] reveal that exohedral derivatives are more favored. Furthermore, the obtained ground-state structure exhibits significant stability, as judged by its larger adsorption energy (1.16 eV) and a larger HOMO-LUMO gap (0.57 eV). The simulated photoelectron spectra (PES) of [Formula: see text] isomers will be instructive to identify the structures in future experiments. There are three interesting discoveries in the present paper: (1) O2 undergoes chemical adsorption onto the parent [Formula: see text] clusters, but the amount of the adsorption energy is related to the parent [Formula: see text] clusters; (2) the process that O2 undergoes dissociative adsorption onto the parent [Formula: see text] clusters is exothermic; (3) [Formula: see text] isomers show smaller X-A energy gaps than those of parent [Formula: see text] clusters, reflecting that their geometric and electronic structures are distorted remarkably due to dissociative adsorption of O2.

Structural and electronic properties of exohedrally doped neutral silicon clusters LnSin (n = 5, 10; Ln = Sm, Eu, Yb).

Lanthanide-doped silicon clusters have been extensively studied in the fields of optoelectronics, magnetism and nanomaterials during the last decade. Herein, systematic structure searches for typical neutral clusters of lanthanide-doped silicon clusters LnSin (n = 5, 10; Ln = Sm, Eu, Yb) have been performed by means of density functional theory coupled with the "stochastic kicking" global search technique. It is found that the Ln atom in LnSin prefers to locate on the surface of Sin to form an exohedral structure, and this exohedral configuration may dominate the nascent structure of LnSin. The spin density and Mulliken population analyses indicate that LnSin clusters possess remarkable magnetic moments (except for YbSin), which are mainly supplied by the Ln 4f electrons (except for Yb). Density of states visually shows the significant spin polarization for open-shell structures of SmSin and EuSin. As for the YbSin (n = 5, 10) system, it has a closed-shell electronic structure with a large HOMO-LUMO gap of 2.72 eV. Bonding analysis, including localized orbital locator and electron density difference, shows that the Si-Si covalent interaction and Sm-Si electrostatic interaction are important for the structural stability of LnSin.

The stability, electronic, and magnetic properties of rare-earth doped silicon-based clusters.

The rare-earth doped silicon-based clusters exhibit remarkable structural, physical, and chemical properties, which make them attractive candidates as building units in designing of cluster-based materials with special optical, electronic, and magnetic properties. The structural, stability, electronic, and magnetic properties of pure silicon Sin + 1 (n = 1-9) and rare-earth doped clusters SinEu (n = 1-9) are investigated using the "stochastic kicking" (SK) global search technique combined with density functional theory (DFT) calculations. It was found that: 1) the ground state structures of pure silicon clusters tend to form compact structures rather than cages with the increase of cluster size; 2) the ground state structures for doped species were found to be additional or substitutional sites, and the rare-earth atoms tend to locate on the surface of the silicon clusters; 3) the average binding energy of the doped clusters increased gradually and exhibited the final phenomenon of saturation with the increase of clusters size. The average binding energy of doped clusters was slightly higher than that of pure silicon clusters of the same size, which indicated that the rare-earth atom encapsulated by silicon enhanced the stability of the silicon clusters to some degree; 4) the doped clusters have strong total magnetic moments, which mainly originated from the contribution of rare-earth atoms, whereas the contribution of silicon atoms were almost negligible. As the cluster size increased, the total magnetic moments of binary mixed clusters tended to be stable.

Stabilization of golden cages by encapsulation of a single transition metal atom.

Golden cage-doped nanoclusters have attracted great attention in the past decade due to their remarkable electronic, optical and catalytic properties. However, the structures of large golden cage doped with Mo and Tc are still not well known because of the challenges in global structural searches. Here, we report anionic and neutral golden cage doped with a transition metal atom MAu16 (M = Mo and Tc) using Saunders 'Kick' stochastic automation search method associated with density-functional theory (DFT) calculation (SK-DFT). The geometric structures and electronic properties of the doped clusters, MAu16q (M = Mo and Tc; q = 0 and -1), are investigated by means of DFT theoretical calculations. Our calculations confirm that the 4d transition metals Mo and Tc can be stably encapsulated in the Au16- cage, forming three different configurations, i.e. endohedral cages, planar structures and exohedral derivatives. The ground-state structures of endohedral cages C2v Mo@Au16--(a) and C1 Tc@Au16--(b) exhibit a marked stability, as judged by their high binding energy per atom (greater than 2.46 eV), doping energy (0.29 eV) as well as a large HOMO-LUMO gap (greater than 0.40 eV). The predicted photoelectron spectra should aid in future experimental characterization of MAu16- (M = Mo and Tc).

Probing the stability of neutral and anionic transition-metal-doped golden cage nanoclusters: M@Au16 (M = Sc, Ti, V).

The golden Au16(q) (q = 0, -1) cage is doped systematically with an external atom of different valence electrons: Sc, Ti, and V. The structural, electronic, and magnetic properties of the doped clusters, M@Au16(q) (M = Sc, Ti and V; q = 0, -1) are investigated using the Saunders "Kick" (SK) global search technique combined with density-functional theory (DFT) calculations (SK-DFT). It is found that the closeness of the calculated vertical/adiabatic detachment energy for Ti-doped and V-doped (3.09/3.16 eV for Ti-doped, and 3.31/3.38 eV for V-doped) is consistent with the negligible geometry change between the anionic and neutral ground state structures. The characteristics of the Sc@Au16(-) cluster includes its remarkably high average binding energy and doping energy, which reflects its high stability. The different spectral features between doped M@Au16(-) and pure Au16(-) clusters indicate endohedral structures with larger distortion from the parent Au16(-) cage for the doped clusters. The s electrons of the Au16 cage are observed to transfer to Sc, Ti and V atom for doped M@Au16(q) clusters by natural population analysis (NPA). The magnetic moment of the impurity Sc/Ti/V atom is somewhat quenched. Furthermore, the electron localization function analysis does not reveal strong interactions. The current work shows that the electronic properties of the golden cage can be systematically tuned through doping.

Probing the structural and electronic properties of small vanadium dioxide clusters by density functional theory and comparison with experimental photoelectron spectroscopy.

The structural evolution and bonding of a series of early transition-metal dioxide clusters, V(n)O(2)(q)(n = 3-9, q = 0, -1), have been investigated using density functional theory (DFT) calculations and the results are compared with experimental literature data. For each vanadium dioxide cluster, many low-lying isomers are generated using the Saunders "Kick" global minimum stochastic search method. Theoretical electron detachment energies (both vertical and adiabatic) were compared with the experimental measurements to verify the ground states of the vanadium dioxide clusters obtained from the DFT calculations. Five kinds of dissociative adsorption configurations of ground-state structure of V(n)O(2)(q) are identified. The dissociative adsorption of O(2) on V(n)(-1, 0) is more favorable than O(2) molecular adsorption. Furthermore, the adsorption energy of O(2) is higher than that of a single atom on the bare V(n)(-1, 0) clusters, but less than twice the adsorption energy for an atom, indicating that O(2) being adsorbed on vanadium clusters are more difficult than single O atom adsorbed on vanadium clusters.

Probing the structural and electronic properties of small vanadium monoxide clusters.

The structural evolution and bonding of a series of early transition-metal oxide clusters, V(n)O(q) (n = 3-9, q = 0,-1), have been investigated with the aid of previous photoelectron spectroscopy (PES) and theoretical calculations. For each vanadium monoxide cluster, many low-lying isomers are generated using the Saunders "Kick" global minimum stochastic search method. Theoretical electron detachment energies (both vertical and adiabatic) were compared with the experimental measurements to verify the ground states of the vanadium monoxide clusters obtained from the DFT calculations. The results demonstrate that the combination of photoelectron spectroscopy experiments and DFT calculation is not only powerful for obtaining the electronic and atomic structures of size-selected clusters, but also valuable in resolving structurally and energetically close isomers. The second difference energies and adsorption energies as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. The adsorption energies of one O atom on the anionic (6.64 → 8.16 eV) and neutral (6.41 → 8.13 eV) host vanadium clusters are shown to be surprisingly high, suggesting strong capabilities to activate O by structural defects in vanadium oxides.

Structural, electronic and magnetic effects of Al-doped niobium clusters: a density functional theory study.

The application of the ab initio stochastic search procedure with Saunders "kick" method has been carried out for the elucidation of global minimum structures of a series of Al-doped clusters, Nb(n)Al (1 ≤ n ≤ 10). We have studied the structural characters, growth behaviors, electronic and magnetic properties of Nb(n)Al by the density functional theory calculations. Unlike the previous literature reported on Al-doped systems where ground state structures undergo a structural transition from the Al-capped frame to Al-encapsulated structure, we found that Al atom always occupies the surface of Nb(n)Al clusters and structural transition does not take place until n = 10. Note that the fragmentation proceeds preferably by the ejection of an aluminum atom other than niobium atom. According to the natural population analysis, charges always transfer from aluminum to niobium atoms. Furthermore, the magnetic moments of the Nb(n)Al clusters are mainly located on the 4d orbital of niobium atoms, and aluminum atom possesses very small magnetic moments.

Probing the structural and magnetic properties of transition metal-benzene anion complexes.

Two types of transition metal-benzene anion complexes, (titanium)(n)(benzene)(m)⁻ and (cobalt)(n)(benzene)(m)⁻ (n ≤ 2, m ≤ 3) have been determined using density functional theory. The photoelectron spectra of Ti(n)Bz(m)⁻ and Co(n)Bz(m)⁻ (n ≤ 2, m ≤ 3) were discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of several low-energy isomers obtained by the structural optimization procedure. The binding of Ti and Co atoms to benzene molecules is accounted by 3d-π bonds, as revealed by the molecular orbitals. The topology of the electronic density has been analyzed, suggesting that the C-C bonds were weakened in the transition metal-benzene complexes in comparison to those in free benzene. Spin density distribution results show the spin densities for Ti(n)Bz(m)⁻ and Co(n)Bz(m)⁻ (n ≤ 2, m ≤ 3) reside mainly on the metal Ti and Co centers (70%-90%). A shift to lower magnetic moment with respect to the pure titanium/cobalt cluster anions indicates the solvent benzene molecule acts to demagnetize the bare titanium/cobalt cluster anions.

Density functional study of structural and electronic properties of bimetallic copper-gold clusters: comparison with pure and doped gold clusters.

The geometrical structures, relative stabilities, and electronic properties of small bare gold clusters Au(n)(lambda) and bimetallic complexes of bare metal clusters with one copper atom Au(n-1)Cu(lambda) (charge lambda = 0, +1, -1; 2 < or = n < or = 9) have been systematically investigated by means of first-principles density functional calculations at the B3LYP level. The results show that the most stable isomers have a planar structure and resemble pure gold clusters in shape, and no three-dimensional isomers were obtained for neutral and anionic doped gold clusters. However, the geometries of Au(n-1)Cu(+) are found to undergo a structural change from two dimensional to three dimensional when the cluster contains 7 atoms. The calculated dissociation energy and second difference energy as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. Ionization potentials and electron detachment energies (both vertical and adiabatic) of Au(n)(lambda) and Au(n-1)Cu(lambda) clusters are discussed and compared with available experimental results. A good agreement between experimental and theoretical results suggests good prediction of the lowest energy structures for all clusters calculated in the present study.

Structural, electronic, and magnetic properties of gold cluster anions doped with zinc: Au(n)Zn- (2 < or = n < or = 10).

The geometrical structures, relative stabilities, electronic, and magnetic properties of zinc-doped gold cluster anions Au(n)Zn(-) (2 < or = n < or = 10) have been systematically investigated by means of first-principles density functional calculations at the B3LYP level. The results show that the most stable isomers have a planar structure and resemble pure gold cluster anions in shape, and no 3D isomers were obtained. Calculated dissociation energy, the second difference energy, and the highest occupied-lowest unoccupied molecular orbital gaps as a function of the cluster size exhibit a pronounced even-odd alternation phenomenon. The first vertical detachment energy of the anion clusters were calculated and compared with available experimental results. A good agreement between experimental and theoretical results suggests good prediction of the lowest-energy structures for all clusters calculated in the present study. Furthermore, both the local and total magnetic moments display a pronounced odd-even oscillation with the number of gold atoms.