Surface-induced melting of metal nanoclusters

We investigate the size effect on melting of metal nanoclusters by molecular dynamics simulation and thermo dynamic theory based on Kofman's melt model. By the minimization of the free energy of metal nanoclusters with respect to the thickness of the surface liquid layer, it has been found that the nanoclusters of the same metal have the same premelting temperature T-pre = T-0 - T-0(gamma(su) - gamma(lv) - gamma(sl))/(rhoLxi) (T-0 is the melting point of bulk metal, gamma(sv) the solid-vapour interfacial free energy, gamma(sl) the liquid-vapour interfacial free energy, gamma(sl),l the solid-liquid interfacial free energy, p the density of metal, L the latent heat of bulk metal, and xi the characteristic length of surface-interface interaction) to be independent of the size of nanoclusters, so that the characteristic length of a metal can be obtained easily by T-pre, which can be obtained by experiments or molecular dynamics (MD) simulations. The premelting temperature T-pre of Cu is obtained by AID simulations, then xi is obtained. The melting point T-cm is further predicted by free energy analysis and is in good agreement with the result of our MD simulations. We also predict the maximum premelting-liquid width of Cu nanoclusters with various sizes and the critical size, below which there is no premelting.

Theoretical study of magnetism, structure and chemical order in transition-metal alloy clusters

Research on transition-metal nanoalloy clusters composed of a few atoms is fascinating by their unusual properties due to the interplay among the structure, chemical order and magnetism. Such nanoalloy clusters, can be used to construct nanometer devices for technological applications by manipulating their remarkable magnetic, chemical and optical properties. Determining the nanoscopic features exhibited by the magnetic alloy clusters signifies the need for a systematic global and local exploration of their potential-energy surface in order to identify all the relevant energetically low-lying magnetic isomers. In this thesis the sampling of the potential-energy surface has been performed by employing the state-of-the-art spin-polarized density-functional theory in combination with graph theory and the basin-hopping global optimization techniques. This combination is vital for a quantitative analysis of the quantum mechanical energetics. The first approach, i.e., spin-polarized density-functional theory together with the graph theory method, is applied to study the Fe$_m$Rh$_n$ and Co$_m$Pd$_n$ clusters having $N = m+n \leq 8$ atoms. We carried out a thorough and systematic sampling of the potential-energy surface by taking into account all possible initial cluster topologies, all different distributions of the two kinds of atoms within the cluster, the entire concentration range between the pure limits, and different initial magnetic configurations such as ferro- and anti-ferromagnetic coupling. The remarkable magnetic properties shown by FeRh and CoPd nanoclusters are attributed to the extremely reduced coordination number together with the charge transfer from 3$d$ to 4$d$ elements. The second approach, i.e., spin-polarized density-functional theory together with the basin-hopping method is applied to study the small Fe$_6$, Fe$_3$Rh$_3$ and Rh$_6$ and the larger Fe$_{13}$, Fe$_6$Rh$_7$ and Rh$_{13}$ clusters as illustrative benchmark systems. This method is able to identify the true ground-state structures of Fe$_6$ and Fe$_3$Rh$_3$ which were not obtained by using the first approach. However, both approaches predict a similar cluster for the ground-state of Rh$_6$. Moreover, the computational time taken by this approach is found to be significantly lower than the first approach. The ground-state structure of Fe$_{13}$ cluster is found to be an icosahedral structure, whereas Rh$_{13}$ and Fe$_6$Rh$_7$ isomers relax into cage-like and layered-like structures, respectively. All the clusters display a remarkable variety of structural and magnetic behaviors. It is observed that the isomers having similar shape with small distortion with respect to each other can exhibit quite different magnetic moments. This has been interpreted as a probable artifact of spin-rotational symmetry breaking introduced by the spin-polarized GGA. The possibility of combining the spin-polarized density-functional theory with some other global optimization techniques such as minima-hopping method could be the next step in this direction. This combination is expected to be an ideal sampling approach having the advantage of avoiding efficiently the search over irrelevant regions of the potential energy surface.

Encapsulation of transition metal species into zeolites and molecular sieves as redox catalysts: Part I-preparation and characterisation of nanosized TiO2, CdO and ZnO semiconductor particles anchored in NaY zeolite

In this paper, we report the preparation and characterisation of nanometer-sized TiO2, CdO, and ZnO semiconductor particles trapped in zeolite NaY. Preparation of these particles was carried out via the traditional ion exchange method and subsequent calcination procedure. It was found that the smaller cations, i.e., Cd2+ and Zn2+ could be readily introduced into the SI′ and SII′ sites located in the sodalite cages, through ion exchange; while this is not the case for the larger Ti species, i.e., Ti monomer [TiO]2+ or dimer [Ti2O3]2+ which were predominantly dispersed on the external surface of zeolite NaY. The subsequent calcination procedure promoted these Ti species to migrate into the internal surface of the supercages. These semiconductor particles confined in NaY zeolite host exhibited a significant blue shift in the UV-VIS absorption spectra, in contrast to the respective bulk semiconductor materials, due to the quantum size effect (QSE). The particle sizes calculated from the UV-VIS optical absorption spectra using the effective mass approximation model are in good agreement with the atomic absorption data.

Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

Transition metal layered double hydroxides for energy storage

Various types of layered double hydroxides, a type of clay, were synthesised. They were then electrochemically tested to determine whether the samples would be suitable to store energy as supercapacitors. A manganese aluminium layered double hydroxide was electrochemically tested for the first time and found to have a large capacitance.

Metal-Ion-Dependent Oxidative DNA Cleavage by Transition Metal Complexes of a New Water-Soluble Salen Derivative

A new water-soluble, salen [salen = bis(salicylidene) ethylenediamine]-based ligand, 3 was developed. Two of the metal complexes of this ligand, i.e., 3a, [Mn(III)] and 3b, [Ni(II)], in the presence of cooxidant magnesium monoperoxyphthalate (MMPP) cleaved plasmid DNA pTZ19R efficiently and rapidly at a concentration similar to 1 mu M. In contrast, under comparable conditions, other metal complexes 3c, [Cu(II)] or 3d, [Cr(III)] could not induce any significant DNA nicking. The findings with Ni(II) complex suggest that the DNA cleavage processes can be modulated by the disposition of charges around the ligand.

Transition metal complexes of a potential anticancer quinazoline ligand

A new heterocycle, namely 2-(furyl)-3-(furfuralimino)-1,2-dihydroquinazolin-4(3H)-one (ffdq) was formed by the ondensation of 2-aminobenzoylhydrazide with furfural and characterized by physico-chemical, spectroscopic, and single crystal X-ray diffraction studies. A series of complexes of ffdq have been synthesized and characterized by physico-chemical, spectroscopic, and thermal studies. According to the i.r. and 1H-n.m.r. spectra ffdq behaves as a bidentate ligand coordinating through quinazoline oxygen and azomethine nitrogen. The FAB-mass spectrum of the Cd(II) complex indicates the monomeric nature of this complex. The X-band e.p.r. spectrum of the Cu(II) complex and thermal stabilities of the Co(II) and Ni(II) complexes are discussed.

Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Action of Transition Metal Oxides on Composite Solid Propellants

The catalytic effects of Fe2O3, Ni2O3, MnO2, and Co2O3 transition metal oxides (TMO) on the combustion of polystyrene and carboxyl-terminated polybutadiene were investigated. The order of activity of TMO's was explained by the presence of Co and absence of Fe and Ni in their lattice systems along with a reduced electron-transfer process; in systems which induce the metal ions to enter the lattice, the electron transfer process is much greater. The thermal decomposition of ammonium perchlorate propellants was enhanced to a greater extent by Co2O3 and MnO2 than by Fe2O3 and Ni2O3.

Interaction of carbon monoxide with transition metal surfaces

XPS studies of the interaction of carbon monoxide with surfaces of Fe, Co and Ni indicate that at 300 K, the disproportionation reaction is prominent up to exposures of 103 L giving rise to high surface concentrations of carbon. At higher exposures and higher temperatures, dissociation of carbon monoxide accompanied by the formation of surface oxide layers becomes more prominent. In the case of copper, disproportionation is prominent up to 104 L even at 500 K followed by dissociation at higher exposures. These results are also supported by Auger spectroscopic studies.

X-ray absorption spectra of niobium dichalcogenides and their first-row transition-metal intercalates

X-ra!. K-absorption spectra of niobium in niobium dichalcogenides. namely NbS, and NbSe, and their first-row transition-metal intercalates Mi P 3N bSz (M = Cr. Mn. Fe. Co. Ni) and Ml#,NbSe2 (M = Fe. CO). have been measured together with those in niobium metal. The spectra of these materials are \er? similar to one another. They reflect the transitions to the partially filled niobium d band with some p character. A bariety of x-ray absorption nearedge structures (XASES) associated with the K edges of intercalated atoms are also presented and discussed.

Satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds

An attempt has been made at synthesis and in resolving some of the uncertainties related to the assignments of charge-transfer satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds. New satellites are reported in the ligand core-hole spectra as well as in the metal core-level spectra of oxides of second- and third-row transition metals including rare earths. Satellites in the ligand levels and the metal levels tend to be mutually exclusive, a behaviour that can be understood on the basis of metal-ligand overlap. Systematics in the intensities and energy separations of satellites in the first-row transition-metal compounds have been examined in order to gain an insight into the nature of these satellites. A simple model involving the sudden approximation has been employed to explain the observed systematics in intensities of satellites appearing next to metal and ligand core levels on the basis of metal-ligand overlap.

Studies on vacuum pyrolysis of ammonium perchlorate and ammonium perchlorate/polystyrene propellant in the presence of transition metal oxides

Vacuum pyrolysis of ammonium perchlorate (AP) and ammonium perchlorate/polystyrene (PS) propellant has been studied by differential thermal analysis (DTA) in order to observe the effect of transition metal oxides on sublimation. Sublimation and decomposition being competitive processes, their proportions depend on the pressure of the pyrolysis chamber. The enthalpies for complete decomposition and complete sublimation are available from the literature and by using these data together with DTA area measurements, the extents of sublimation and decomposition have been calculated for AP and the propellant system. The effect of the metal ions on the extent and rate of sublimation depends on their nature. For AP the extent of sublimation increases with a decrease in particle size. For the propellants the powder sublimes more readily than the bulk material, but in the presence of metal ions the bulk material sublimes more readily than the powder. To substantiate this finding, the effect of MnO2 on AP sublimation as a function of particle size was examined, and it was observed that the extent of sublimation decreases as the particle size decreases.