Sandeep Nigam

Structural and electronic properties of Sin,Sin+, and AlSin−1 (n=2–13) clusters: Theoretical investigation based on ab initio molecular orbital theory

The geometric and electronic structures of Sin, Sin+, and AlSin−1 clusters (2⩽n⩽13) have been investigated using the ab initio molecular orbital theory under the density functional theory formalism. The hybrid exchange-correlation energy function (B3LYP) and a standard split-valence basis set with polarization functions [6-31G(d)] were employed for this purpose. Relative stabilities of these clusters have been analyzed based on their binding energies, second difference in energy (Δ 2E) and fragmentation behavior. The equilibrium geometry of the neutral and charged Sin clusters show similar structural growth. However, significant differences have been observed in the electronic structure leading to their different stability pattern. While for neutral clusters, the Si10 is magic, the extra stability of the Si11+ cluster over the Si10+ and Si12+ bears evidence for the magic behavior of the Si11+ cluster, which is in excellent agreement with the recent experimental observations. Similarly for AlSin−1 clusters...

CO Oxidation by BN−Fullerene Cage: Effect of Impurity on the Chemical Reactivity

Using state of the art spin-polarized density functional theory it is found that a chemically inert (BN)(36) cluster can be activated by incorporating magnetic nanoparticles inside it. To illustrate this aspect we have calculated the geometries and electronic structure of Fe(BN)(36) and Fe(4)(BN)(36) clusters, which showed the appearance of gap states localized on the impurity atoms. The reaction of O(2) molecules with these clusters results in weak interaction and an elongation of the O-O bond. Further interaction of this complex species with an incoming CO molecule leads to the formation of CO(2). The reaction mechanism has been investigated via Langmuir-Hinshelwood and Elay-Rideal routes, and the minimum energy path calculations are performed using the elastic band method. These results have implications in designing novel materials based on metal nanoparticles for potential applications as industrial catalyst.

Structural and electronic properties of Sin, Sin−, and PSin−1 clusters (2⩽n⩽13): Theoretical investigation based on ab initio molecular orbital theory

The geometric and electronic structures of Si(n), Si(n)-, and PSi(n-1) clusters (2 < or = n < or = 13) have been investigated using the ab initio molecular orbital theory formalism. The hybrid exchange-correlation energy functional (B3LYP) and a standard split-valence basis set with polarization functions (6-31+G(d)) were employed to optimize geometrical configurations. The total energies of the lowest energy isomers thus obtained were recalculated at the MP2/aug-cc-pVTZ level of theory. Unlike positively charged clusters, which showed similar structural behavior as that of neutral clusters [Nigam et al., J. Chem. Phys. 121, 7756 (2004)], significant geometrical changes were observed between Si(n) and Si(n)- clusters for n = 6, 8, 11, and 13. However, the geometries of P substituted silicon clusters show similar growth as that of negatively charged Si(n) clusters with small local distortions. The relative stability as a function of cluster size has been verified based on their binding energies, second difference in energy (Delta2 E), and fragmentation behavior. In general, the average binding energy of Si(n)- clusters is found to be higher than that of Si(n) clusters. For isoelectronic PSi(n-1) clusters, it is found that although for small clusters (n < 4) substitution of P atom improves the binding energy of Si(n) clusters, for larger clusters (n > or = 4) the effect is opposite. The fragmentation behavior of these clusters reveals that while small clusters prefer to evaporate monomer, the larger ones dissociate into two stable clusters of smaller size. The adiabatic electron affinities of Si(n) clusters and vertical detachment energies of Si(n)- clusters were calculated and compared with available experimental results. Finally, a good agreement between experimental and our theoretical results suggests good prediction of the lowest energy isomeric structures for all clusters calculated in the present study.

Growth Pattern of Agn (n = 1−8) Clusters on the α-Al2O3(0001) Surface: A First Principles Study

We report an extensive first-principles study of the structure and electronic properties of Ag(n) (n = 1-8) clusters isolated in gas phase and deposited on the α-Al(2)O(3) surface. We have used the plane wave based pseudopotential method within the framework of density functional theory. The electron ion interaction has been described using projector augmented wave (PAW), and the spin-polarized GGA scheme was used for the exchange correlation energy. The results reveal that, albeit interacting with support alumina, the Ag atoms prefers to remain bonded together suggesting an island growth motif is preferred over wetting the surface. When compared the equilibrium structures of Ag clusters between free and on alumina substrate, a significant difference was observed starting from n = 7 onward. While Ag(7) forms a three-dimensional (3D) pentagonal bipyramid in the isolated gas phase, on alumina support it forms a planar hexagonal structure parallel to the surface plane. Moreover, the spin moment of the Ag(7) cluster was found to be fully quenched. This has been attributed to higher delocalization of electron density as the size of the cluster increases. Furthermore, a comparison of chemical bonding analysis through electronic density of state (EDOS) shows that the EDOS of the deposited Ag(n) cluster is significantly broader, which has been ascribed to the enhanced spd hybridization. On the basis of the energetics, it is found that the adsorption energy of Ag clusters on the α-Al(2)O(3) surface decreases with cluster size.

An insight into local environment of lanthanide ions in Sr2SiO4:Ln (Ln = Sm, Eu and Dy)

Sr2SiO4 is an important inorganic host for lanthanide-doped white-light-emitting diodes. In order to probe the local structure and symmetry around lanthanide ions in Sr2SiO4, detailed experimental and theoretical investigations have been carried out. Samples prepared via sol–gel methods were thoroughly characterized using X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS) and photoluminescence (PL) spectroscopy. The local symmetries of SrO9 and SrO10 polyhedra were determined using emission spectroscopy with europium as the probe ion. Despite having the same oxidation state and comparable ionic radii, Sm3+, Dy3+ and Eu3+ behave differently in terms of their site occupation at the Sr sites of SrO9 and SrO10 polyhedra. While Eu replaces Sr in both polyhedra, Sm and Dy reside specifically at the 9-coordinated Sr sites only. Based on density functional theory (DFT) calculations, it has been established that for Dy and Sm, the strong metal–oxygen bonding leads to significant distortion and hence the destabilization of MO10 polyhedra in the host.

Theoretical study of aromaticity in inorganic tetramer clusters

Ground state geometry and electronic structure of M42- cluster (M = B, Al, Ga) have been investigated to evaluate their aromatic properties. The calculations are performed by employing the Density Functional Theory (DFT) method. It is found that all these three clusters adopt square planar configuration. Results reveal that square planar M42- dianion exhibits characteristics of multifold aromaticity with two delocalised π-electrons. In spite of the unstable nature of these dianionic clusters in the gas phase, their interaction with the sodium atoms forms very stable dipyramidal M4Na2 complexes while maintaining their square planar structure and aromaticity.

M atom (M = Cu, Ag and Au) interaction with Ag and Au substrates: a first-principles study using cluster and slab models

Using state-of-the-art first-principles calculations we report the interaction of M atoms (M = Cu, Ag and Au) with small Ag(n), Au(n) clusters (n = 3 and 6) and periodic Ag(111) and Au(111) surfaces. All calculations were performed using the plane wave pseudo-potential approach under the spin polarized version of the generalized gradient approximation scheme. The result shows that the equilibrium geometry of all MAg(3) and MAu(3) clusters favor a planar rhombus structure. From the charge distribution analysis of MAg(n)/MAu(n) clusters it is found that, while Cu and Ag donates electronic charge towards the host clusters, the Au atom acts as an acceptor, thus creating charge polarization in the system. The difference in orbital decomposed charges before and after the M interaction reveals that enhanced s-d hybridization is responsible for keeping the MAu(6) cluster planar, and increased p-orbital participation induces three-dimensional configurations in MAg(6) clusters. The optimization of M atom deposition on the Ag(111) and Au(111) surfaces shows that M atoms prefer to adsorb on the threefold fcc site over other well-defined sites. From the orbital decomposed charge analysis it is inferred that, although there is significant difference in the absolute magnitude of the interaction energy between M atoms and the Ag or Au substrates, the nature of chemical bonding is similar for the finite size clusters as well as in slab models.

Novel properties of boron nitride nanotubes encapsulated with Fe, Co, and Ni nanoclusters

Using state of the art spin polarized density functional theory, we report the stability and structural aspects of small magnetic clusters M(4) (M = Fe, Co, and Ni) inside an inert boron nitride nanotube [BNNT(10,0)]. The geometry optimization was carried out starting with various possible configurations [one-dimensional (1D) linear chain, two-dimensional (2D) planar rhombus, and three-dimensional (3D) tetrahedral], and the results reveal that the ground state geometry of M(4) cluster inside the nanotube favors 3D configuration over others. Moreover, these small clusters are found to retain their magnetic nature with a small reduction in the total magnetic moment even after encapsulation. The radial confinement effect on the atomic structure of M(4) clusters was investigated by optimizing the Co(4) (prototype example) in BNNT(10, 0), BNNT(9, 0), and BNNT(8, 0). It is found that with the increase in radial confinement (smaller diameter), the Co(4) cluster becomes more compact, which further leads to significant changes in the electronic and magnetic properties. The electronic density of states analysis of the M(4) clusters inside BNNT(10,0) showed the appearance of additional electronic states in the band gap of BNNT(10, 0). In order to underscore the possibility of functionalizing these encapsulated tubes, we have performed the adsorption of oxygen molecules on it. The adsorption of oxygen in the molecular form with elongated O-O bonds further justifies its application in the oxidative catalysis.

Enhancement of dielectric constant in a niobium doped titania system: an experimental and theoretical study

Gigantic enhancement of relative dielectric permittivity of TiO2 upon doping with niobium is reported here. Dielectric and impedance spectroscopic analysis on these materials indicates a electrically heterogeneous microstructure consisting of semiconducting grains and insulating grain boundaries, leading to formation of numerous micro-capacitors, within the single phase compound. However, the degree of electrical heterogeneity decreases with increase in Nb5+ doping concentration as the Nb5+ starts to get segregated at the grain boundary. In addition to extrinsic electrical heterogeneity, intrinsic defect dipoles also contribute towards the large permittivity. Experimental observation has been rationalized at atomic level using density functional theory (DFT) which reveals that Nb atoms do not favor closer positioning and that the thermodynamically preferable distance between two dopant atoms (Nb atoms) is ∼7 A. Remarkably at this distance the system becomes highly polarized due to occurrence of Ti3+/Nb5+ defects in nearby regions, which in turn leads to a colossal dielectric constant.

Alumina-supported sub-nanometer Pt10 clusters: amorphization and role of the support material in a highly active CO oxidation catalyst

Catalytic CO oxidation is unveiled on size-selected Pt_(10) clusters deposited on two very different ultrathin (≈0.5–0.7 nm thick) alumina films: (i) a highly ordered alumina obtained under ultra-high vacuum (UHV) by oxidation of the NiAl(110) surface and (ii) amorphous alumina obtained by atomic layer deposition (ALD) on a silicon chip that is a close model of real-world supports. Notably, when exposed to realistic reaction conditions, the Pt_(10)/UHV-alumina system undergoes a morphological transition in both the clusters and the substrate, and becomes closely akin to Pt_(10)/ALD-alumina, thus reconciling UHV-type surface-science and real-world experiments. The Pt_(10) clusters, thoroughly characterized via combined experimental techniques and theoretical analysis, exhibit among the highest CO oxidation activity per Pt atom reported for CO oxidation catalysts, due to the interplay of ultra-small size and support effects. A coherent interdisciplinary picture then emerges for this catalytic system.