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Icosahedral Ni13@Ag42 is a stable nanoparticle formed by a magnetic nickel core surrounded by a silver coating that provides physical protection to the 3d metal cluster as well as antibacterial properties. In this work, we report density functional theoretical calculations to delve into a comprehensive analysis of how surface oxidation impacts the structural, electronic, magnetic, and reactivity properties of this interesting nanoparticle. To elucidate the role played by the silver coating, we compare the results with those found for the bare Ni13 cluster also subjected to surface oxidation. When Ni13 is covered by silver, we find a markedly robust behavior of the magnetic moment of the resulting nanoparticle, which remains nearly constant upon oxidation up to the rates explored, and the same holds for its overall reactivity. The obtained trends are rationalized in terms of the complex interplay between Ni-Ag and Ag-O interactions which impact the relative inter-atomic distances, charge transfer effects, spin polarization and magnetic couplings.
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Iron ilmenene is a new two-dimensional material that has recently been exfoliated from the naturally occurring iron titanate found in ilmenite ore, a material that is abundant on the earth's surface. In this work, we theoretically investigate the structural, electronic and magnetic properties of 2D transition-metal-based ilmenene-like titanates. The study of magnetic order reveals that these ilmenenes usually present intrinsic antiferromagnetic coupling between the 3d magnetic metals decorating both sides of the Ti-O layer. Furthermore, the ilmenenes based on late 3d brass metals, such as CuTiO3 and ZnTiO3, become ferromagnetic and spin compensated, respectively. Our calculations which include spin-orbit coupling reveal that the magnetic ilmenenes have large magnetocrystalline anisotropy energies when the 3d shell departs from being either filled or half-filled, with their spin orientation being out-of-plane for elements below half-filling of 3d states and in-plane above. These interesting magnetic properties of ilmenenes make them useful for future spintronic applications because they could be synthesized as already realized in the iron case.
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ZnMg alloys of certain compositions in the Zn-rich side of the phase diagram are particularly efficient, and widely used, as anticorrosive coatings, but a sound understanding of the physico-chemical properties behind such quality is still far from being achieved. The present work focuses on the first stage of the corrosion process, namely the initial growth of a sacrificial surface oxide layer, whose characteristics will condition the next stages of the corrosion. A comprehensive ab initio study, based on density functional theory, is carried out on ZnMg nanoalloys with 20 atoms and different compositions, which serve as model systems to simulate the complex processes that occur in extended granular surfaces. The structural and electronic properties, when progressive oxidation of the nanoalloys takes place, are analyzed in detail with the help of structural descriptors, energetic descriptors such as the oxygen adsorption energies and excess adsorption energies, as well as with electronic ones based on the topological analysis of the electron density and the electron localization function, from which a detailed analysis of the bonding patterns is extracted. We explain why small amounts of Mg create a very positive synergy between Zn and Mg that increases the reactivity to oxygen while reducing, at the same time, the stress induced on the cluster substrate, both facts working in favor of promoting the growth of the oxide crust whilst protecting the core. Moreover, we also show that stoichiometries close to the Mg2Zn11 and MgZn2 compositions are the best candidates to optimize the protection against corrosion in Zn-Mg alloys, in agreement with the experimental observations.
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Due to quantum confinement effects, the understanding of iron oxide nanoparticles is a challenge that opens the possibility of designing nanomaterials with new capacities. In this work, we report a theoretical density functional theory study of the structural, electronic, and magnetic properties of neutral and charged iron oxide clusters FenOm0/± (n = 1-6), with m values until oxygen saturation is achieved. We determine the putative ground state configuration and low-energy structural and spin isomers. Based on the total energy differences between the obtained global minimum structure of the parent clusters and their possible fragments, we explore the fragmentation channels for cationic oxides, comparing with experiments. Our results provide fundamental insight on how the structural pattern develops upon oxidation and its connection with the magnetic couplings and net total moment. Upon addition of oxygen, electronic charge transfer from iron to oxygen is found which weakens the iron-iron bond and consequently the direct exchange coupling in Fe. The binding energy increases as the oxygen ratio increases, rising faster at low oxidation rates. When molecular oxygen adsorption starts to take place, the binding energy increases more slowly. The oxygen environment is a crucial factor related to the stabilities and to the magnetic character of iron oxides. We identified certain iron oxide clusters of special relevance in the context of magnetism due to their high stability, expected abundance and parallel magnetic couplings that cause large total magnetic moments even at high oxidation ratios.
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Transition-metal oxide nanoparticles are relevant for many applications in different areas where their superparamagnetic behavior and low blocking temperature are required. However, they have low magnetic moments, which does not favor their being turned into active actuators. Here, we report a systematical study, within the framework of the density functional theory, of the possibility of promoting a high-spin state in small late-transition-metal oxide nanoparticles through alloying. We investigated all possible nanoalloys An-xBxOm (A, B = Fe, Co, Ni; n = 2, 3, 4; 0≤x≤n) with different oxidation rates, m, up to saturation. We found that the higher the concentration of Fe, the higher the absolute stability of the oxidized nanoalloy, while the higher the Ni content, the less prone to oxidation. We demonstrate that combining the stronger tendency of Co and Ni toward parallel couplings with the larger spin polarization of Fe is particularly beneficial for certain nanoalloys in order to achieve a high total magnetic moment, and its robustness against oxidation. In particular, at high oxidation rates we found that certain FeCo oxidized nanoalloys outperform both their pure counterparts, and that alloying even promotes the reentrance of magnetism in certain cases at a critical oxygen rate, close to saturation, at which the pure oxidized counterparts exhibit quenched magnetic moments.
RESUMO
We report a comprehensive theoretical study of the structural and electronic properties of neutral and charged nickel oxide clusters, NinOm0/± (n = 3-8 and m = 1-10), in the context of recent experiments of photodissociation and Ion Mobility Mass Spectrometry. By means of density functional theory calculations in the generalized gradient approximation for exchange and correlation, we determined the putative ground states as well as the low-energy structural- and spin-isomers which were then used to explore the favorable fragmentation channels of the nickel oxide cationic clusters, and the resulting most abundant products, in good qualitative agreement with photodissociation measurements. Apart from stoichiometries different from those of their nickel oxide macroscopic counterparts, we found a tendency to form compact Ni subclusters, with reentrance of low-coordinated structures close to the equiatomic Ni-O concentration, taking the form of alternating Ni-O rings in the smaller sizes, in good qualitative agreement with Ion Mobility Mass Spectrometry measurements. This structural pattern is manifested in a drop of the total spin magnetic moment close to the equiatomic concentration due to the formation of antiparallel magnetic couplings. Although antiparallel couplings are found to a more or less extent in most clusters, especially in the oxygen rich phase, we identified certain clusters of special interest in the context of magnetic grains because of their large total magnetic moment and abundance. There are even some nickel oxide clusters with a higher total moment than their pure Ni counterparts, due to parallel magnetic couplings and the contribution of the oxygen atoms to the total moment.
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The favorable stoichiometry of Co(n)O(m)(+) clusters has been recently determined by means of multiphoton dissociation of oxide cluster beams coming from laser evaporation of metal rods seeded with 0.5-5% oxygen and selected by time of flight mass spectroscopy. It was observed that the prominent stoichiometry is n = m, and that the preferred dissociation channel is the loss of O2 molecules. The Co4O4(+) cluster is found to be particularly abundant, an indication of its high stability. In this work we present density functional calculations, within the generalized gradient approximation, for the geometric, electronic, and magnetic properties of neutral and cationic Co(n)O(m)(0/+) clusters with n = 3-8 and m = 1-10. The ionic structures were determined after optimizing several initial geometries selected from previous calculations of pure Co clusters, with consecutive adsorbed oxygen atoms, as well as geometries constructed by assembling several CoO units and adding subsequent oxygen atoms. The fragmentation patterns were studied by comparing the energy separation of O2, CoO, Co2O, CoO2, and Co fragments. We obtain that the preferred fragmentation channel is the loss of O2, that the favourable stoichiometry is 1 : 1, and that Co4O4(+) is especially stable, in full agreement with the experiments. In addition the magnetic properties related to spin isomeric configurations of (CoO)n(+) clusters are studied in detail.
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Using the density functional method with the generalized gradient approximation for the exchange and correlation, we investigated the geometrical and electronic properties of free-standing complexes of Con clusters combined with hydrogen-saturated boron-nitrogen (BN) rings [(BN)3H6]m. The Co atoms tend to form a subcluster capped by BN rings that preserve the Co subcluster against the environment and with which they weakly interact. Thus, the Co subcluster is capable of sustaining a noticeable magnetic moment. These facts are relevant for designing grains with localized magnetic moments. We also optimized those TMn[(BN)3H6]n complexes with n = 1-3 and TM = Fe, Ni, Ru, Rh, and Pd, starting with the ground-state geometry obtained previously for TM = Co, in order to analyze the dependence of the electronic properties with the number of d electrons in the transition-metal atoms.
