A topological path to the formation of a quasi-planar B70 boron cluster and its dianion.

In view of the competing assignments regarding the most stable isomer of the B70 boron cluster including the quasi-planar and bilayer structures, we reinvestigated the structural motifs of B70 using a genetic algorithm for structure search (MEGA) in conjunction with density functional theory computations using the PBE functional. The quasi-planar structure was also constructed using the topological leapfrog algorithm. The latter search aimed to give us unique insight into its formation and the growth pattern of boron clusters. Also, the di-anionic state of B70 was explored. Our extensive search suggested a competition between the quasi-planar, tubular and bilayer isomers for the ground state of B70 in both neutral and dianionic states. While the bilayer form is more stable in the neutral state, the quasi-planar counterpart becomes more stable in the dianionic B702-. The stability arises due to the fact that the B702- dianion possesses 50 π electrons that satisfy the disk aromaticity model rule. These results tend to extend the stabilization of the quasi-planar structure upon negative charge addition previously found in small size boron clusters to larger sizes.

Formation of the quasi-planar B56 boron cluster: topological path from B12 and disk aromaticity.

Formation and stability of the B56 boron cluster were investigated using a topological approach and the disk aromaticity model. An extensive global energy minimum search for the B56 system which was carried out by means of the Mexican Enhanced Genetic Algorithm (MEGA) in conjunction with density functional theory computations, confirms a quasi-planar structure as its energetically most stable isomer. Such a structural motif is derived by applying a topological leapfrog operation to a B12 form. Its high thermodynamic stability can be explained by the disk aromaticity model in which the delocalization of its π orbitals can be assigned to the levels of a particle in a circular box with the [(1σ)2 (1π)4 (1δ)4 (1φ)4 (2σ)2 (1γ)4 (2π)4 (2δ)4 (1η)4 (2φ)4 (1θ)2] electronic configuration. This π delocalization is confirmed by other delocalization indices. While the B56 has a similar electron delocalization to that of the quasi-planar B50, they have opposite magnetic ring current properties because of the symmetry selection rules of their HOMO-LUMO electronic transitions. The π delocalization in the boron clusters is larger at long distances as compared to carbon clusters at similar sizes, but such a trend is reversed at shorter distances.

Interaction Mechanisms and Interface Configuration of Cysteine Adsorbed on Gold, Silver, and Copper Nanoparticles.

Cysteine-protected metal nanoparticles (NPs) have shown interesting physicochemical properties of potential utility in biomedical applications and in the understanding of protein folding. Herein, cysteine interaction with gold, silver, and copper NPs is characterized by Raman spectroscopy and density functional theory calculations to elucidate the molecular conformation and adsorption sites for each metal. The experimental analysis of Raman spectra upon adsorption with respect to free cysteine indicates that while the C-S bond and carboxyl group are similarly affected by adsorption on the three metal NPs, the amino group is sterically influenced by the electronegativity of each metal, causing a greater modification in the case of gold NPs. A theoretical approach that takes into consideration intermolecular interactions using two cysteine molecules is proposed using a S-metal-S interface motif anchored to the metal surface. These interactions generate the stabilization of an organo-metallic complex that combines gauche (PH) and anti (PC) rotameric conformers of cysteine on the surface of all three metals. Similarities between the calculated Raman spectra and experimental data confirm the thiol and carboxyl as adsorption groups for gold, silver, and copper NPs and suggest the formation of monomeric "staple motifs" that have been found in the protecting monolayer of atomic-precise thiolate-capped metal nanoclusters.

Effect of the Metal-Ligand Interface on the Chiroptical Activity of Cysteine-Protected Nanoparticles.

Gold, silver, and copper small nanoparticles (NPs), with average size ≈2 nm, are synthesized and afterward protected with l- and d-cysteine, demonstrating emergence of chiroptical activity in the wavelength range of 250-400 nm for all three metals with respect to the bare nanoparticles and ligands alone. Silver-cysteine (Ag-Cys) NPs display the higher anisotropy factor, whereas gold-cysteine (Au-Cys) NPs show optical and chiroptical signatures slightly more displaced to the visible range. A larger number of circular dichroism (CD) bands with smaller intensity, as compared to gold and silver, is observed for the first time for copper-cysteine (Cu-Cys) NPs. The manifestation of optical and chiroptical responses upon cysteine adsorption and the differences between the spectra corresponding to each metal are mainly dictated by the metal-ligand interface, as supported by a comparison with calculations of the oscillatory and rotatory strengths based on time-dependent density functional theory, using a metal-ligand interface motif model, which closely resembles the experimental absorption and CD spectra. These results are useful to demonstrate the relevance of the interface between chiral ligands and the metal surfaces of Au, Ag, and Cu NPs, and provide evidence and further insights into the origin of the transfer mechanisms and induction of extrinsic chirality.

Structures, stabilities and aromatic properties of endohedrally transition metal doped boron clusters M@B22, M = Sc and Ti: a theoretical study.

A genetic search algorithm in conjunction with density functional theory calculations was used to determine the lowest-energy minima of the pure B22 cluster and thereby to evaluate the capacity of its isomers to form endohedrally doped cages with two transition metal atoms M (M = Sc and Ti). An important charge transfer from metal atoms M to the boron cage takes place, stabilizing the endohedral compounds, as predicted with the genetic algorithm implemented. High-level coupled-cluster theory CCSD(T) calculations were carried out to confirm that the structures found are the lowest-energy isomers. For a deeper understanding of the doping effects and related charge transfer, the best structural motif of the B22 isomers was also determined when the bare cages are in anionic states, such as B222- and B224-. It was found that B22 has an appropriate size, geometric shape and electronic state to host the chosen metal atoms and, consequently, to form stable endohedrally doped compounds Ti@B22 (C2v, 4-Ti) and Sc@B22 (C2v, 5-Sc). The chemical bonding was analyzed in order to understand the molecular orbitals that these novel systems form. The cage aromaticity was evaluated by means of the nuclear independent chemical shift (NICS(0)iso) indices, the isochemical shielding surface (ICSSzz), the anisotropy of the current induced density (ACID) maps, and the magnetic ring current Gauge-Including Magnetically Induced Current (GIMIC) method, indicating that aromaticity plays a crucial role in the stabilization of endohedrally doped boron clusters. Finally, the thermodynamic stability of the latter, using parameters derived from density functional theory (DFT), was evaluated. Ab initio molecular dynamics (AIMD) simulations were performed to elucidate the stability, at high temperature, of the most stable endohedrally doped boron clusters 4-Ti and 5-Sc.

CeO2(111) electronic reducibility tuned by ultra-small supported bimetallic Pt-Cu clusters.

Controlling Ce4+ to Ce3+ electronic reducibility in a rare-earth binary oxide such as CeO2 has enormous applications in heterogeneous catalysis, where a profound understanding of reactivity and selectivity at the atomic level is yet to be reached. Thus, in this work we report an extensive DFT-based Basin Hopping global optimization study to find the most stable bimetallic Pt-Cu clusters supported on the CeO2(111) oxide surface, involving up to 5 atoms in size for all compositions. Our PBE+U global optimization calculations indicate a preference for Pt-Cu clusters to adopt 2D planar geometries parallel to the oxide surface, due to the formation of strong metal bonds to oxygen surface sites and charge transfer effects. The calculated adsorption energy values (Eads) for both mono- and bimetallic systems are of the order of 1.79 up to 4.07 eV, implying a strong metal cluster interaction with the oxide surface. Our calculations indicate that at such sub-nanometer sizes, the number of Ce4+ surface atoms reduced to Ce3+ cations is mediated by the amount of Cu atoms within the cluster, reaching a maximum of three Ce3+ for a supported Cu5 cluster. Our computational results have critical implications on the continuous understanding of the strong metal-support interactions over reducible oxides such as CeO2, as well as the advancement of frontier research areas such as heterogeneous single-atom catalysts (SAC) and single-cluster catalysts (SCC).

Formation of the quasi-planar B50 boron cluster: topological path from B10 and disk aromaticity.

The lowest-lying isomer of the B50 boron cluster is confirmed to have a quasi-planar shape with two hexagonal holes. By applying a topological (leap-frog) dual operation followed by boron capping, we demonstrated that such a quasi-planar structure actually comes from the smallest elongated B102-, and its high thermodynamic stability is due to its inherent disk aromaticity arising from its 32 valent π electrons that fully occupy a disk configuration of [(1σ)2(1π)4(1δ)4(2σ)2(1φ)4(2π)4(1γ)4(2δ)4(1η)4]. The aromatic character of the quasi-planar B50 is further supported by a strong diatropic magnetic current flow. The sudden appearance of a quasi-planar B50 again points out that the growth pattern of pure boron clusters is still far from being completely understood.

Stability of AumAgn (m + n = 1-6) clusters supported on a F-center MgO(100) surface.

A theoretical study has been performed for deposited AumAgn (m + n = 1-6) clusters. The combined use of the Mexican Enhanced Genetic Algorithm (MEGA) and Density Functional Theory (DFT) calculations allows us to explore the potential energy surface and therefore, find the global minimum configuration for each composition. We have performed calculations of clusters deposited on defects (oxygen vacancies) known as F centers on MgO (100) surfaces. Our results show interesting differences in the geometries of the clusters upon deposition and as a consequence in their electronic properties. The combination of two metals with different electronegativities creates an inhomogeneous charge distribution on their exposed surface producing good conditions for a catalytic process to take place.

A comparative study of AumRhn (4 ≤ m + n ≤ 6) clusters in the gas phase versus those deposited on (100) MgO.

A comparative theoretical study has been performed of the gas phase and deposited AumRhn (4 ≤ m + n ≤ 6) clusters. The combined use of a genetic algorithm and Density Functional Theory (DFT) calculations allows us to explore the potential energy surface and, therefore, find efficiently and automatically the global minimum configuration for each composition. Our results show interesting effects on the geometries of the clusters on deposition. This occurs because the rhodium atoms (electronically) prefer to be in contact with the MgO surface, sometimes promoting planar clusters to become three-dimensional when deposited, and three-dimensional clusters in the gas phase to become two-dimensional. Together with the change in geometries, the magnetic moment is reduced from the gas phase, as the electrons rearrange themselves when the cluster interacts with the substrate.

Ab initio and anion photoelectron study of AunRhm (n = 1-7, m = 1-2) clusters.

Anion photoelectron spectroscopy (PES) and ab initio calculations have been used to identify the unique structural, electronic, and magnetic properties of both neutral and anionic binary AunRhm (n = 1-7 and m = 1-2) clusters in vacuo. Negative ion photoelectron spectra are presented with electron binding energies measured up to 3.493 eV. We discuss our computational results in the context of the PES experiment, in which the calculated electron affinities and vertical detachment energies are in good agreement with the measured values. Theoretically, we investigate the low-lying energy structures and the spin isomers of each neutral, anionic and cationic species. The PES spectra, binding energies, fragmentation energy, electron affinities, vertical and adiabatic detached energies, HOMO-LUMO (H-L) gaps and vibrational spectra are presented and discussed. Our results show that the characteristic planarity for gold clusters is preserved for many of the bimetallic clusters. This study is therefore compared with the case of pure gold for which ample experimental and theoretical data are available. Both experimental and theoretical results obtained here are compared and discussed with previous theoretical studies on the same systems.