[CuSnSb] as a dual spherical-spherical aromatic heterometallic cluster bridged an antiaromatic CuSn motif.

The formation of [CuSnSb] serves as a template for heterometallic species to evaluate the resulting aromatic properties. Our results indicated that the spherical aromatic characteristics of the [CuSnSb] building unit remained in the overall aggregate, featuring an induced shielding cone from different orientations of the external field. Furthermore, the isostructural and isoelectronic [Sn] cluster sustained similar characteristics, which supported the notion of a direct relationship between [CuSnSb] and [Sn] cluster dimers.

Cuboctahedral Pd as a spherical aromatic noble metal core: insights from a ligand-protected [Pd(Tr)] cluster.

Low-valent palladium nanoparticles are efficient species promoting catalytic activity and selectivity in a number of chemical reactions. Recently, an atom-centered cuboctahedral Pd motif has been characterized as a ligand-protected [Pd(Tr)] cluster featuring a 1s superatomic shell structure. In this report, we describe the ligand-cluster of and endohedral-cage interaction in [Pd(Tr)], which accounts for a favorable situation in the overall cluster.

New global minimum conformers for the Pt and Pt clusters: low symmetric species featuring different active sites.

Context: The study of platinum (Pt) clusters and nanoparticles is essential due to their extensive range of potential technological applications, particularly in catalysis. The electronic properties that yield optimal catalytic performance at the nanoscale are significantly influenced by the size and structure of Pt clusters. This research aimed to identify the lowest-energy conformers for Pt , Pt , and Pt species using Density Functional Theory (DFT).

Intercluster B-H and B-B aggregation in iso- and -[BH]. Spherical aromaticity in borane dimers.

The formation of molecular-based functional materials is a key step towards the development of technologies at the nanoscale. Recently, it has been shown that after oxidation of -[BH] anions, an induced aggregation of two cluster units is achieved, retaining their parent B backbones as persistent building blocks. Such characterization provides an interesting scenario to further understand relevant factors leading to aggregation in a minimal structure involving two units.

Exploration of Free Energy Surface of the Au Nanocluster at Finite Temperature.

The first step in comprehending the properties of Au clusters is understanding the lowest energy structure at low and high temperatures. Functional materials operate at finite temperatures; however, energy computations employing density functional theory (DFT) methodology are typically carried out at zero temperature, leaving many properties unexplored. This study explored the potential and free energy surface of the neutral Au nanocluster at a finite temperature, employing a genetic algorithm coupled with DFT and nanothermodynamics.

On the variation of cluster core characteristics by an endohedral atom. Shape variation in 8-ce [EAu(PPh)] (E = N, P, As, Sb) clusters.

Atomically precise gold superatoms have attracted interest owing to their suitable use as building blocks for cluster-assembled materials, favoring ordered structures with advanced properties. In this sense, expanding their versatility is a relevant issue for controlling their properties and retaining a specific nuclearity. Interestingly, the reported structure for isoelectronic [AuN(PPh)] and [AuSb(PPh)] clusters denotes two contrasting shapes featuring a tetrahedral and square pyramidal structure, respectively.

On the halide aggregation into the [Au(PPh)] cluster core. Insights from structural, optical and interaction energy analysis in [(PhPAu)X] and [(PhPAu)X] species (X = Cl, Br, I).

The aggregation of halide atoms into gold clusters offers an interesting scenario for the development of novel metal-based cavities for anion recognition and sensing applications. Thus, further understanding of the different contributing terms leading to efficient cluster-halide aggregation is relevant to guide their synthetic design. In this report, we evaluate the formation of [(PhPAu)X] and [(PhPAu)X] species (X = Cl, Br, I) in terms of different energy contributions underlying the stabilization of the cluster-halide interaction, and the expected UV-vis absorption profiles as a result of the variation in frontier orbital arrangements.

Intermediate Intercluster Bond Orders. Electronic Communication in Au(SR) Superatomic Molecules.

Ligand-protected gold clusters remain potential building blocks for envisaged molecular materials. The archetypal Au(SR) cluster can be viewed as a robust template for the fusion of two Au(SR) cluster units, retaining a bi-icosahedral Au core. Via electrochemical properties, the overall charge state can be selectively tuned, enabling the access of 14 valence electron (ve) species featuring a single intercluster bond and nearby charge from -1 to +3, achieving related species bearing 15- to 11-ve with variable intercluster bond orders.

Ligand-free supermolecules: [Pd@Ge] and [Pd@Sn] as multiple-bonded Zintl-ion clusters based on Pd@Ge and Pd@Sn assembled units.

Understanding intercluster bonding interactions is important in the rational synthesis of building blocks for molecular materials. Such characteristics have been developed for coinage metal clusters resembling single-, double-, and triple-bonded species, coined as supermolecules. Herein, we extend such an approach for understanding main-group clusters, thus evaluating [Pd@E] clusters (E = Ge, Sn) involving the fusion of parent spherical aromatic [Pd@E] building units.

[Ag(Sn-Sn)] and [(η-Sn)Ag(η-Sn)], as aggregates of spherical aromatic building blocks. Persistence of aromaticity upon cluster gathering.

Formation of cluster-based materials requires a fundamental understanding of the resulting cluster aggregation processes. The Sn Zintl-ion structure can be viewed as a building block featuring a spherical aromatic species, leading to a cluster gathering upon oxidative coupling and/or mediated by transition metals. Here, we evaluate the spherical aromatic properties of [Sn-Sn], [Ag(Sn-Sn)] and [(η-Sn)Ag(η-Sn)], as aggregates of two Sn building units held together oxidative coupling and mediated by a Ag(I) transition metal center.

On the structure and electronic properties of Pt clusters: new most stable structures for = 16-17.

The lowest energy structures and electronic properties of Pt clusters up to = 17 are investigated by using a genetic algorithm in combination with density functional theory calculations. There are several putative global minimum structures for platinum clusters which have been reported by using different approaches, but a comprehensive study for = 15-17 has not been carried out so far. Herein, we perform a consensus using GGA (PBE), meta-GGA (TPSS) and hybrid (B3PW91, PBE0, PBEh-3c, M06-L) functionals in conjunction with the Def2-TZVP basis set.

Antifungal activity of Co(II) and Cu(II) complexes containing 1,3-bis(benzotriazol-1-yl)-propan-2-ol on the growth and virulence traits of fluconazole-resistant Candida species: synthesis, DFT calculations, and biological activity.

Relevant virulence traits in Candida spp. are associated with dimorphic change and biofilm formation, which became an important target to reduce antifungal resistance. In this work, Co(II) complexes containing a benzotriazole derivative ligand showed a promising capacity of reducing these virulence traits.

Cl@SiX cages: evaluation of encapsulation nature, structural rigidity, and Si-NMR patterns using relativistic DFT calculations.

The experimental characterization of Cl@Si endohedral clusters, featuring different ligands such as [Cl@SiH] (1) [Cl@SiHCl] (2), and [Cl@SiCl] (3), provides insight into the variable encapsulation environment for chloride anions. The favorable formation of such species enables the evaluation of the encapsulation nature and the role of the inner anion in the rigidity of the overall cluster. Our results show a sizable interaction which increases as -66.

Correction: Structure effects of Pt clusters for the oxygen reduction reaction: first-principles calculations.

Correction for 'Structure effects of Pt clusters for the oxygen reduction reaction: first-principles calculations' by Peter L. Rodríguez-Kessler , , 2023, https://doi.org/10.

Structure effects of Pt clusters for the oxygen reduction reaction: first-principles calculations.

In the present work, the lowest energy structures and electronic properties of Pt clusters are investigated using molecular dynamics simulations. The results showed that the most stable configuration is a capped pyramidal structure, which is 0.8 kal mol lower in energy than a layered structure previously reported [V.

Structural and electronic properties for Be-doped Pt ( = 1-12) clusters obtained by DFT calculations.

In this work, we have performed a computational study on the structure and electronic properties for Be-doped Pt ( = 1-12) clusters in the framework of density functional theory (DFT). The most stable structures of the clusters are obtained by a structure search procedure based in simulated annealing. The results show that the PtBe clusters adopt compact structure motifs with Be situated at the edge sites while only in PtBe the Be atom occupies the center site.

Relative Populations and IR Spectra of Cu Cluster at Finite Temperature Based on DFT and Statistical Thermodynamics Calculations.

The relative populations of Cu isomers depend to a great extent on the temperature. Density functional theory and nanothermodynamics can be combined to compute the geometrical optimization of isomers and their spectroscopic properties in an approximate manner. In this article, we investigate entropy-driven isomer distributions of Cu clusters and the effect of temperature on their IR spectra.

Nature of hydride and halide encapsulation in Ag cages: insights from the structure and interaction energy of [Ag(X){SP(OPr)}] (X = H, F, Cl, Br, I) from relativistic DFT calculations.

Unraveling the different contributing terms to an efficient anion encapsulation is a relevant issue for further understanding of the underlying factors governing the formation of endohedral species. Herein, we explore the favorable encapsulation of hydride and halide anions in the [Ag(X){SP(OPr)}] (X = H, 1, F, 2, Cl, 3, Br, 4, and, I, 5) series on the basis of relativistic DFT-D level of theory. The resulting Ag-X interaction is sizable, which decreases along the series: -232.

Evaluation of ultrasmall coinage metal M(dppe) M = Cu, Ag, and Au clusters. Bonding, structural and optical properties from relativistic DFT calculations.

Ultrasmall ligand-protected clusters are prototypical species for evaluating the variation at the bottom of the nanoscale range. Here we explored the ultrasmall gold-phosphine M(dppe) cluster, as a prototypical framework to gain insights into the fundamental similarities and differences between Au, Ag, and Cu, in the 1-3 nm size range, via relativistic DFT calculations. Different charge states involving 8- and 10-cluster electron (ce) species with a 1S1P and 1S1P1D configuration, leading to structural modification in the Au species between Au(dppm) and Au(dppm), respectively.

Coinage-metal pillarplexes hosts. Insights into host-guest interaction nature and luminescence quenching effects.

Host-guest chemistry is a relevant issue in materials science, which encourages further development of versatile host structures. Here the particular features of coinage-metal pillarplexes are evaluated towards formation of host-guest aggregates by the inclusion of 1,8-diaminooctane, as characterized for [M8(LMe)2]4+ (M = Ag, and, Au). The obtained results denotes the main contribution from van der Waals type interaction (50%), followed by a contribution from orbital polarization and electrostatic nature (20% and 30%), involving both orbitalary and electrostatic terms.

On Heteronuclear Isoelectronic Alternatives to [Au(dppe)Cl]: Electronic and Optical Properties of the 18-Electron Os@[Au(dppe)Cl] Cluster from Relativistic Density Functional Theory Computations.

The development of well-defined atomically precise heteronuclear nanoclusters passivated by protecting ligands is presently a booming area, owing to the fact that doping well-known homonuclear nanostructures allows fine-tuning of their properties. Here, we explore by means of density functional theory calculations the possibility of doping the central gold atom in the classical [Au(dppe)Cl]cluster () by Os. Although both [Au(dppe)Cl] and [Os@Au(dppe)Cl] have the same total number of electrons, we show that they are not isoelectronic within the formalism of the superatom model, being respectively an 8- and an 18-electron species.

On the structure and reactivity of PtCu (n = 1-7) alloy clusters.

The structure, electronic and reactivity properties of PtCu (n = 1-7) clusters are investigated in the framework of density functional theory (DFT). The most stable forms of the clusters are obtained by a structure search procedure based in simulated annealing. The results show that the PtCu cluster alloys adopt layered structure motifs with segregation of the Cu and Pt species.

Systematic cluster growth: a structure search method for transition metal clusters.

The systematic cluster growth (SCG) method is a biased structure search strategy based on a seeding process for investigating the structural evolution and growth pattern of transition metal clusters. In SCG, a set of initial structures with size n are constructed based on the equilibrium structures of the preceding n- 1 cluster isomers by adding a single atom at all inequivalent binding sites. This strategy requires a relatively low number of evaluations for global minima localization on the potential energy surface, allowing its application in first-principles calculations.

Structural characterization, reactivity, and vibrational properties of silver clusters: a new global minimum for Ag.

In the present work, the lowest energy structures and electronic properties of Agn clusters up to n = 16 are investigated using a successive growth algorithm coupled with density functional theory calculations (DFT). In the literature, a number of putative global minimum structures for silver clusters have been reported by using different approaches, but a comparative study for n = 15-16 has not been undertaken so far. Here, we perform a comparative study using the PW91/cc-pVDZ-PP level to more precisely determine the optimal configuration.