Magnetism of small V clusters embedded in a Cu fcc matrix: an ab initio study

We present extensive first principles density functional theory (DFT) calculations dedicated to analyze the magnetic and electronic properties of small V _n clusters (n = 1, 2, 3, 4, 5, 6) embedded in a Cu fcc matrix. We consider different cluster structures such as: (i) a single V impurity, (ii) several V₂ dimers having different interatomic distance and varying local atomic environment, (iii) V₃ and (iv) V₄ clusters for which we assume compact as well as 2- and 1-dimensional atomic configurations and finally, in the case of the (v) V₅ and (vi) V₆ structures we consider a square pyramid and a square bipyramid together with linear arrays, respectively. In all cases, the V atoms are embedded as substitutional impurities in the Cu network. In general, and as in the free standing case, we have found that the V clusters tend to form compact atomic arrays within the cooper matrix. Our calculated non spin-polarized density of states at the V sites shows a complex peaked structure around the Fermi level that strongly changes as a function of both the interatomic distance and local atomic environment, a result that anticipates a non trivial magnetic behavior. In fact, our DFT calculations reveal, in each one of our clusters systems, the existence of different magnetic solutions (ferromagnetic, ferrimagnetic, and antiferromagnetic) with very small energy differences among them, a result that could lead to the existence of complex finite-temperature magnetic properties. Finally, we compare our results with recent experimental measurements.     

Bonding in Cu,Ag, and Au clusters: relativistic effects,trends, and surprises

Electronic structure and bonding in anionic coinage metal clusters are investigated via density-functional calculations, focusing on an extensive set of isomers of Cu(-)(7), Ag(-)(7), and Au(-)(7). While the ground states of Cu(-)(7) and Ag(-)(7) are three dimensional (3D), that of Au(-)(7) is planar, separated from the optimal 3D isomer by 0.5 eV. The simulated thermally weighted photoabsorption spectrum of Au(-)(7) is dominated by planar structures, and it agrees well with the measured one. The propensity of Au(-)(N) clusters to favor planar structures (with N as large as 13) is correlated with strong hybridization of the atomic 5d and 6s orbitals due to relativistic effects.     

Magnetic anisotropy and magnetization dynamics of Fe nanoparticles embedded in Cr and Ag matrices

Static and dynamical magnetic properties of Fe nanoparticles (NPs) embedded in non-magnetic (Ag) and antiferromagnetic (Cr) matrices with a volume filling fraction (VFF) of 10% have been investigated. In both Fe@Ag and Fe@Cr nanocomposites, the Fe NPs have a narrow size distribution, with a mean particle diameter around 2 nm. In both samples, the saturation magnetization reaches that of Fe bulk bcc, suggesting the absence of alloying with the matrices. The coercivity at 5 K is much larger in Fe@Cr than in Fe@Ag as a result of the strong interaction between the Fe NPs and the Cr matrix. Temperature-dependent magnetization and ac-susceptibility measurements point out further evidence of the enhanced interparticle interaction in the Fe@Cr system. While the behaviour of Fe@Ag indicates the presence of weakly interacting magnetic monodomain particles with a wide distribution of blocking temperatures, Fe@Cr behaves like a superspin glass produced by the magnetic interactions between NPs.     

笼状Au20内掺M13(M=Fe,Ti)团簇磁性的密度泛函计算研究

采用密度泛函理论中的广义梯度近似方法,对M13(M =Fe,Ti)以及M13内掺Au20团簇的几何结构和磁性进行了计算研究.结果表明:M13和M13内掺Au20团簇的几何结构在0.006-0.05nm误差范围内保持着Ih对称性.Fe13团簇最低能态的总磁矩为44μB,内掺到Au20笼中后形成的Fe13内掺Au20团簇的最低能态总磁矩为38μB,且Au原子与内掺Fe13团簇之间存在着弱铁磁相互作用.Ti13团簇在总磁矩为6μB时能量最低,掺入Au20笼后形成的Ti13内掺Au20团簇最低能态总磁矩是4μB,内表面12个Ti原子与表面Au壳之间是弱铁磁相互作用,而与中心Ti原子之间是弱反铁磁相互作用.由于Au20笼状外壳的影响,Fe13内掺Au20和Ti13内掺Au20团簇中Fe13和Ti13的磁矩比无金壳的Fe13和Ti13团簇的磁矩分别减少了6.81μB和2.88μB.     

Magnetism of Fe clusters and islands on Pt surfaces

Clusters and islands of Fe atoms have been prepared by noble gas buffer layer assisted growth as well as by standard molecular beam epitaxy on Pt substrates. Xe buffer layers have been utilized to promote the formation of compact, relaxed Fe clusters with narrow size distribution. Without the Xe buffer, strained Fe islands with a characteristic misfit dislocation network are formed. Magnetization loops obtained by magneto-optical Kerr effect measurements reveal that in-plane easy magnetization axis is only found for the relaxed clusters, pointing out the important role of epitaxial lattice deformations for the magnetic anisotropy. PACS 61.46.+w; 68.37.Ef; 36.40.Cg; 75.75.+a     

Effect of hydrostatic pressure on the static susceptibility of the spin-glass systems Ag:Mn,Au:Mn,Cu:Mn and Au:Fe

Previous studies of the magnetic susceptibility of a Ag-3 at.% Mn spin-glass under high pressure are extended to include the systems Au-3at.% Mn, Cu-3at.% Mn and Au-3at.% Fe. In all four alloys the spin-glass freezing temperatureT ₀ increases with pressure, yielding the volume dependences lnT ₀/ lnV=–3.6±0.4, –4.1±0.6, –2.1±0.4 and –1.64±0.25, respectively. These results give information about the nature of the interaction mechanisms responsible for the spin-glass freezing phenomena. The pressure dependence of the Curie temperature of ferromagnetic Au-20at.% Fe was also studied.Dedicated to B. Mühlschlegel on the occasion of his 60th birthday     

M2Al2(M=Au,Ag,Cu)混合小团簇的密度泛函研究

采用基于密度泛函理论的B3LYP方法,利用小核实赝势LANL2DZ,优化了含重金属二元混合团簇M2Al2(M=Au,Ag,Cu)的稳定结构,并得出具有C2v(1A1)对称性的蝴蝶结构比平面构型更加稳定,其中团簇Au2Al2最稳定.计算了稳定结构的结合能、电离势、电子亲和能、最高占据轨道能级和最低空轨道能级及二者间的能隙,得出参杂团簇M2Al2比非参杂团簇M4(M=Au,Ag,Cu)更稳定的结论.     

Superconductivity in α-phase alloys of Cu,Ag and Au

We have found f.c.c. alloys rich in noble metals to be superconducting. From these data, extrapo lated values for the transition temperatures of Au, Ag and Cu can be obtained.     

Theoretical determination of the surface excitation parameter for Ti, Fe, Cu, Pd, Ag, and Au

The angular dependence of the surface excitation parameter (SEP) is theoretically determined for different materials (Ti, Fe, Cu, Pd, Ag, and Au) for angles to the surface normal between 10° and 70° and for energies between 300 and 3400 eV. The method is based on analysis of energy-differential inelastic electron scattering cross sections calculated from the dielectric function with the software QUEELS (quantitative analysis of electron energy losses at surfaces) valid for reflection-electron-energy-loss spectroscopy (REELS). The calculations presented here are closely related to a method previously developed [N. Pauly, S. Tougaard, F. Yubero, Surf. Interf. Anal. 37 (2005) 1151] for materials (like Al and Si) with a clear surface plasmon peak. However, for the materials studied here the excitations are broad and there is no clear visual distinction between surface and bulk excitations. It is therefore not possible, as in the previous studies of Al and Si, to isolate the intensity of the surface excitation directly. Therefore the volume component for an infinite medium is subtracted from the calculated cross section and in this way the surface excitation component of the cross section is determined and the SEP calculated.     

Recoil energies of fragments photoproduced in Cu,Ag and Au

The recoil energies of²⁴Na produced in Cu, Ag and Au and of a series of fragments produced in Cu irradiated with 800 MeV bremsstrahlung have been measured in directions forward, backward and perpendicular to the beam using the thick target-thick catcher method. Comparison of the measured values with theoretical calculations indicates that²⁴Na is produced through fission in Ag and Au and that fission is competing with spallation even in Cu.     

Ultraviolet laser ionization studies of 1-fluoronaphthalene clusters and density functional theory calculations

This paper studies supersonic jet-cooled 1-fluoronaphthalene(1FN) clusters by ultraviolet(UV) laser ionization at 281 nm in a time-of-flight mass spectrometer.The(1FN) + n(n=1-3) series cluster ions are observed where the signal intensity decreases with increasing cluster size.The effects of sample inlet pressures and ionization laser fluxes to mass spectral distribution are measured.Using density functional theory calculations,it obtains a planar geometric structure of 1FN dimer which is combined through two hydrogen bonds.The mass spectra indicate that the intensity of 1FN trimer is much weaker than that of 1FN dimer and this feature is attributed to the fact that the dimer may form the first "shell" in geometric structure while the larger clusters are generated based on this fundamental unit.     

Virtual bound states of Pd in Cu,Ag and Au and of Pt in Ag

The positions and widths of the virtual bound states of 5 and 10% Pd in Cu, Ag and Au and of 5 and 10% Pt in Ag have been measured by XPS. The spin—orbit splitting of the Pt state in Ag is reduced from the theoretical value, but comparable to the spectroscopic atomic value. The host lattice d-band structure is perturbed in the alloys.     

Molecular dynamics study of configuration and stability of vacancy clusters in fcc Ag

Vacancies may agglomerate to form vacancy Frank loops of different shapes, as observed by transmission electron microscopy in quenched and irradiated fcc metals. The dynamics for the dissociation of vacancy Frank loops and the subsequent evolution of defect nanostructures were explored by means of the molecular dynamics method and displayed by the local crystalline order method. Frank loops of different initial shapes were found to transform to a variety of defect nanostructures: triangle to stacking fault tetrahedra, equilateral hexagon to quasi-heptahedron, and scalene hexagon to various intermediate structures depending on the length of the short side. The formation energies for vacancy Frank loops of different geometries are introduced to categorize various final configurations. Crystallographic analysis and elasticity calculations were performed to elucidate the transform mechanisms in fcc Ag.     

M_2Ga(M=Cu,Ag,Au)二元合金小团簇的从头算研究(英文)

根据原子与分子反应静力学和群论理论推导出二元合金小团簇M2Ga(M=Cu,Ag,Au)的离解极限和基态电子态.采用量子力学从头算方法及小核实赝势和相应的基组,对二元合金小团簇M2Ga进行几何优化,得到M2Ga基态(2B2)为弯曲平面型结构,并与单元团簇M3(M=Cu,Ag,Au)相似.计算得到合金团簇比单元团簇稳定,其中Au2Ga体系最稳定.同时给出谐振频率、力常数,并且分析得到电子相关效应使得团簇更加紧凑、稳定性增强.     

Embedded cluster calculations for hydrogen chemisorption on the (111) surfaces of fcc Co,Ni, Cu,Rh, Pd and Ag

We present a muffin tin based calculation on (TM)₃H, (TM)₇H and (TM)₁₉H clusters embedded at the surface of an effective jellium-like medium whose potential is treated in scattering length approximation. We consider the changes occurring when the d-like perturbation of the TM muffin tins is switched on. The broad chemisorption-induced resonance seen for H on the effective jellium surface is narrowed and shifted down in energy. Furthermore the occupation of this resonance is increased from about 1.1 electrons to about 1.4 (on 3d metals) or 1.8 (on 4d metals), due to d-like states dropping down from the d band to form a relatively welldefined “bonding state”. An antibonding state containing about 0.4 electrons is formed at the top of the d band. The results are compared with other calculations and with photoemission data. Implications for the metal-hydrogen distance and (for Ni) the demagnetizing effect of hydrogen chemisorption are discussed. We use the change in total single particle energy when the d-like perturbation is switched on to estimate trends in chemisorption energy along the 3d and 4d series. In the 3d case experimental data is available on the difference in chemisorption energy between Ni and Cu which is in reasonable agreement with our estimate.     

Nuclear spin-lattice relaxation of dilute Mn in Cu,Ag, and Au

We have developed a new method of determining nuclear spinlattice relaxation times of dilute impurity nuclei in non-magnetic host metals. Direct measurement of these extremely rapid relaxation times has hitherto been difficult. The present method is based on fast pulsed heating of a sample containing oriented radioactive nuclei and is applicable to a wide range of impurity-host combinations and over a large range of applied magnetic fields. Results are presented for extremely dilute Mn in noble metal hosts.     

Electric field gradients in dilute alloys of Cu,Ag and Au

In this paper we present perturbed angular correlation (PAC) measurements on¹⁰⁰Rh and¹¹¹Cd in a number of dilute alloys of Cu, Ag and Au. We discuss the electric field gradient (EFG) values derived from these and other experiments in the framework of a theory of the EFG at nearest neighbours of point defects in metals, essentially based on the screening of a point charge in a free electron gas. We include in our discussion the EFG due to a neighbour monovacancy for a number of fcc metals.     

Transport in fullerene device coupled to Cu,Ag and Au electrodes

We present an ab initio approach of the electronic transport through a single molecular junction based on C₂₀ fullerene. The electronic properties of a single molecular junction constrained within two semi-infinite metallic electrodes are largely affected by the choice of electrode material. The two-probe device formed by the mechanically control break technique has been modelled with three distinct electrode materials from group IB of the periodic table, namely copper, silver and gold. The quantum characteristics of these mechanically stable devices are obtained by utilising first-principle density functional theory together with non-equilibrium green function method. We evaluate the quantum characteristics, namely density of states, transmission spectrum, energy levels, current and conductance, which essentially determine the behaviour of a molecule linked to different electrodes. Our investigation concludes that copper, silver and gold electrode configuration in conjunction with C₂₀ fullerene behaves as metallic, non-metallic and semi-metallic in nature, respectively.