Mössbauer study of a novel series of ternary rare-earth iron-rich intermetallics: ND(Fe1-xTi x )6+y(x ∼ 0.1 and 0≤y≤5)

A study of the Nd-Fe-Ti phases at the Fe-rich end of the phase diagram has been carried out using⁵⁷Fe Mössbauer spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX). In particular,⁵⁷Fe Mössbauer spectroscopy has been used to characterize the phases present in these samples. In addition to the two well-known 217 and 112 phases, twonovel phases have been identified, with compositions denoted by3–29 and9–94, which are closely linked to the orthorhombic ScFe₆Ga₆-type and the hexagonal TbCu₇-type structures, respectively. The possible crystal structures of these new phases will be discussed in terms of the dumbbell substitution sequence in the CaCu₅ structure.     

Density functional study on the bimetallic Ti_mZr_n(n+m ≤ 5) clusters and their interactions with H_2

Equilibrium geometries, stabilities, and electronic properties of small Ti_mZr_n(n + m ≤ 5) clusters were investigated using the density functional method. The ground states were determined, and it was found that the larger clusters and those consisting of more Zr atoms are more stable. The electronic properties of the clusters were discussed based on HOMO-LUMO gaps, vertical ionization potentials(VIP), and vertical electron affinities(VEA). Furthermore, we studied the interactions between those clusters and molecular hydrogen, and found that in all the cases dissociative chemisorptions occurred. According to the chemisorption energies, the pure Zr clusters are relatively more active towards H_2 when compared with the others except Ti_3Zr, which shows the highest activity. The magnetic moments of Ti_mZr_n and Ti_mZr_nH_2 were also compared, and the results show that the hydrogenated clusters have the same or decreased total magnetic moments with respect to the bare clusters except for Ti_3Zr_2.     

Density functional theory study of neutral AlS_n(n=2-9) clusters

This paper investigates the geometrical structures and relative stabilities of neutral AlS n(n = 2-9) using the density functional theory.Structural optimisation and frequency analysis are performed at the B3LYP/6-311G(d) level.The ground state structures of the AlS n show that the sulfur atoms prefer not only to evenly distribute on both sides of the aluminum atom but also to form stable structures in AlS n clusters.The structures of pure S n are fundamentally changed due to the doping of the Al atom.The fragmentation energies and the second-order energy differences are calculated and discussed.Among neutral AlS n(n = 2-9) clusters,AlS 4 and AlS 6 are the most stable.     

Critical behavior of La0.67−y (Sr, Ba, Ca)0.33+y Mn1−x Sn x O3 (x = 0.01, 0.02, y = 0, 0.07) perovskites

The magnetic critical behavior of the manganese perovskite series $ {\text{La}}_{{0.67 - y}} {\left( {{\text{Sr,}}\,\,{\text{Ba,}}\,\,{\text{Ca}}} \right)}_{{0.33 + y}} {\text{Mn}}_{{1 - x}} {\text{Sn}}_{x} {\text{O}}_{3} The magnetic critical behavior of the manganese perovskite series (x = 0.01, 0.02, y = 0, 0.07) is studied by means of dc magnetic measurements and ¹¹⁹Sn M?ssbauer spectroscopy. The structure can be described by a rhombohedral unit cell (space group R–3C) for the samples where the A-site is occupied by La and Sr or La and Ba ions and orthorhombic unit cell (space group Pnma) for the samples where the A-site is occupied by La and Ca ions. Arrott and scaling plots show that the samples, where the A-site is occupied by La and Sr or La and Ba ions, follow the behavior of a conventional second-order ferromagnetic transition. In contrast, the samples that contain La and Ca ions in the A-site show anomalous behavior around Curie point. M?ssbauer measurements show two magnetic phases below T _c. One of them exhibits stronger exchange interactions with more rapid electron transfer between Mn³⁺/Mn⁴⁺, compared to the other.     

Density functional theory study of Mg_2Ni_n(n= 1–8) clusters

The density functional theory B3PW91 with LANL2DZ basis sets has been used to study the possible geometries of Mg2Nin(n = 1–8) clusters. For the lowest energy structures of the clusters, stabilities, electronic properties, and natural bond orbital(NBO) are calculated and discussed. The results show that the doped Mg atoms reduce the stabilities of pure Ni clusters. The Mg2Ni2, Mg2Ni4, and Mg2Ni6clusters are more stable than neighboring clusters. The system appears magic number characteristics. In addition, the hybridization phenomenon occurs, owing to the interaction of Mg and Ni. The result of charge transfer is that Ni atom is negative and the Mg atom is positive. We also conclude that the 3p and 4d orbitals of the Ni atom have an effect on the stabilities of the clusters.     

Density functional theory study of MgnNi2 （n=1-6） clusters

The geometries of Mg n Ni 2(n = 1-6) clusters are studied by using the hybrid density functional theory(B3LYP) with LANL2DZ basis sets.For the ground-state structures of Mg n Ni 2 clusters,the stabilities and the electronic properties are investigated.The results show that the groundstate structures and symmetries of Mg clusters change greatly due to the Ni atoms.The average binding energies have a growing tendency while the energy gaps have a declining tendency.In addition,the ionization energies exhibit an odd-even oscillation feature.We also conclude that n = 3,5 are the magic numbers of the Mg n Ni 2 clusters.The Mg 3 Ni 2 and Mg 5 Ni 2 clusters are more stable than neighbouring clusters,and the Mg 4 Ni 2 cluster exhibits a higher chemical activity.     

Geometrical,electronic, and magnetic properties of Au n V (n = 1–8) clusters: A density functional study

The geometrical, electronic, and magnetic properties of small Au _n V (n?=?1–8) clusters have been investigated using density functional theory at the PW91 level. An extensive structural search indicates that the V atom in low-energy Au _n V isomers tends to occupy the most highly coordinated position and the ground-state configuration of Au _n V clusters favors a planar structure. The substitution of a V atom for an Au atom in the Au _{n +1} cluster transforms the structure of the host cluster. Maximum peaks are observed for the ground-state Au _n V clusters at n?=?2 and 4 for the size dependence of the second-order energy differences, implying that the Au₂V and Au₄V clusters possess relatively higher stability. The energy gap of the Au₃V cluster is the largest of all the clusters. This may be ascribed to its highly symmetrical geometry and closed eight-electron shell. For ground-state clusters with the same spin multiplicity, as the clusters size increases, the vertical ionization potential decreases and the electron affinity increases. Magnetism calculations for the most stable Au _n V clusters demonstrate that the V atom enhances the magnetic moment of the host clusters and carries most of the total magnetic moment.     

Density functional theory study on the structure and properties of Si3N4 clusters

The hybrid density functional theory B3LYP with basis sets 6-31G＊ has been used to study on the equilibrium geometries and electronic structures of possible isomers of Si3N4 clusters. 24 possible isomers are obtained. The most stable isomer of Si3N4 is a 3D structure with 7 Si-N bonds and 2 N-N bonds that could beformed by 3 quadrangles. The bond properties of the most stable isomer was analyzed by using natural bond orbital method （NBO）, the results suggest that the charges on Si and N atoms in Si-N bonds are quite large, so theinteraction of N-Si atoms in Si3N4 cluster is of strongly electric interaction. The primary IR and Raman vibrational frequency located at 1033.40 cm^-1, 473.63 cm^-1 respectively. The polarizabilities and hyperpolarizabilities of the most stable isomer are also analyzed.     

Ferromagnetic resonance study of Y3−z Ca z Fe5−x−y Co x Ge y O12 films

Conclusions It has been found that the character of the magnetic anisotropy changes markedly when the Co + Ge YIG films are doped with calcium. For the induced uniaxial and in-plane anisotropy we observe an increasing departure from the predictions based on the two-parameter model and for the cubic anisotropy the constantK ₁ becomes dependent on the growth direction. As a source for the latter effect the octahedral or tetrahedral preference of Co ions depending on the growth direction may be considered. The measured linewidth proportional to frequency indicates the presence of a relaxation mechanism which is, probably, connected with octahedral Co³⁺ ions.The authors express their thanks to Dr. P. Görnert and M. Neviva for preparation of the LPE films and to Dr. P. Novák for valuable discussions.Dedicated to Jan Kaczér DrSc on the occasion of his 65th birthday.     

Synthesis and characterization of layered perovskite oxides La1 + x Sr2 − x MnCrO7 (x = 0.2, 0.5)

Intergrowth perovskite type complex oxides of composition La_1.2Sr_1.8MnCrO₇ and La_1.5Sr_1.5MnCrO₇ have been synthesized by ceramic method. Rietveld profile analysis shows that the phases crystallize with tetragonal unit cell in the space group I4/mmm. Both the phases behave as insulators in the high temperature region and the linearity of log ρ versus T ^?1/4 plot in the temperature range 150–300 K shows that the electronic conduction occurs by a 3D variable range hopping mechanism. The phases show insulator-metal transition at low temperature which could be due to the mixed valence state of Mn³⁺/Mn⁴⁺ by double exchange mechanism. The ferromagnetic interactions observed for the samples arises from double exchange interaction between Mn ³⁺ and Mn⁴⁺ and Cr³⁺ and Mn³⁺ ions.     

DFT studies on the interaction of PtxRuyMz (M = Fe,Ni, Cu,Mo, Sn,x + y + z = 4, x ≥ 1, y ≥ 1) alloy clusters with O2

The reaction mechanism of O₂ dissociation on Pt_xRu_yM_z (M = Fe, Ni, Cu, Mo, Sn, x + y + z = 4, x ≥ 1, y ≥ 1) alloy catalysts have been investigated with density functional theory calculations in this work. For bare alloy clusters, bimetallic clusters are more stable than the ternary alloy clusters. The geometries of the Pt_xRu_yM_z–O₂ system, O–O bond stretching frequency and electronic-structure details have been investigated. The energies of O₂ adsorption on PtRu clusters are slightly higher than those on Pt_xRu_yM_z clusters, and the more charge transfer to O₂ from the metal cluster, the higher O₂ the adsorption energy obtains. The reaction barriers show that the catalytic performance of trimetallic clusters are better than those of bimetallic clusters, and Pt₂RuM clusters exhibit superior catalytic activity for O₂ dissociation. The different performance of these alloy clusters for O₂ dissociation is scrutinised with aid of molecular orbital and natural bond orbital population analysis.     

Spin-glass behaviour of novel ternary uranium aluminide U3Co4+ x Al12− x (x = 0.55)

Experimental results on dc and ac susceptibility, magnetization and magnetic relaxation, specific heat, electrical resistivity and magnetoresistivity up to 8?T are reported for the novel ternary uranium aluminide U₃Co_4.55Al_11.45. The temperature dependence of the dc susceptibility shows a cusp at a characteristic temperature T _f?=?8–10?K that depends weakly on the applied magnetic field. The observed pronounced difference between the ZFC and FC magnetizations, as well as the decay in the remanent, both give evidence that a highly irreversible, frozen state is formed below T _f which is reminiscent of spin-glass behaviour. The real and imaginary parts of the ac susceptibility show that the corresponding T _f peaks are only slightly dependent on frequency. Electrical resistivity measured at zero and in fields up to 8?T indicates that the Kondo-like state becomes dominant at temperatures above T _f.     

Preparation and dielectric study of high-quality PLZT x/65/35 (x = 6,7,8) ferroelectric ceramics

Ferroelectric ceramics are an important class of solid-state materials as they exhibit a wide range of applications. Various compositions of the ferroelectric ceramic (Pb,La)(Zr,Ti)O₃ (known as PLZT) were prepared and their dielectric properties were studied. It is difficult to prepare phase-pure PLZT compounds by the direct solid-state reaction method. Its preparation required the use of a special 'covering method' adopted to facilitate phase formation using the solid-state reaction method. High-quality PLZT samples of different compositions (x/65/35, x=6,7,8) prepared using the 'covering method' without adding any excess PbO (to avoid PbO loss) resulted in single-phase formation. The 8/65/35 composition has yielded a dielectric constant of 11273 at T_C, which is in good agreement with the literature value [1, 2]. Also, as the lanthanum content x was varied from 6 to 8 mole %, T_C decreased and the low-frequency (1 kHz) room-temperature dielectric constant value increased. The present publication gives a detailed account of the evolution of the phase-pure PLZT compositions and their physical properties.     

Density functional investigation of structural and electronic properties of small bimetallic silver–gold clusters

Structural and electronic properties of bimetallic silver–gold clusters up to eight atoms are investigated by the density functional theory using Wu and Cohen generalized gradient approximation functional. By substitution of Ag and Au atoms, in the optimized lowest energy structures of pure gold and silver clusters, we determine the ground state conformations of the bimetallic silver–gold ones. We reveal that Ag atoms prefer internal positions whereas Au atoms prefer exposed ones favoring charge transfer from Ag to Au atoms. For each size and composition, binding energy, HOMO–LUMO gap, magnetic moment, vertical ionization potential, electron affinity and chemical hardness were calculated. On increasing the size of the cluster by varying number of Ag atoms with fixed number of Au ones, vertical ionization potential and electron affinity show obvious odd–even oscillations consistent with the pure Ag and Au clusters. Au atoms inclusion in the cluster increases the binding energy and vertical ionization potential, indicating higher stability as the number of Au atoms grows. The variation of chemical hardness with the composition in a cluster with the same size shows peaks when the number of Ag atoms is greater than or equal to Au ones, corresponding to transition from planar to tri-dimensional structures. For clusters with even number of atoms, the peaks indicate that the clusters with the same number of Ag and Au atoms are the most stable ones. Analyzing the density of states, we found that increasing the concentration of Ag atoms affects the energy separation between the HOMO and the low lying occupied states.