Polynuclear manganese grids and clusters—A magnetic perspective

High nuclearity paramagnetic, spin-coupled transition metal clusters and grids are fascinating chemists and physicists partly because of their structural beauty, and the challenge of creating them, but also because of their novel physical properties. Magnetic interactions between the spin centers are a primary focus. This review will examine a selection of Mn(II) polynuclear grids and clusters, with nuclearities in the range Mn₄ to Mn₉. Theoretical treatments of the magnetic properties are discussed, and approaches to solving the exchange problem for ‘large’ spin systems related to computational difficulties. A freely available software package (MAGMUN4.1) is presented as a means of dealing simply with spin-coupled clusters in general, and symmetry reduction methods are discussed briefly as a means of dealing with ‘large’ spin systems.     

Magnetic properties of Mn-rich Rh2Mn1+xSn1−x Heusler alloys

X-ray powder diffraction and magnetization measurements have been carried out on Rh₂Mn_1+xSn_1−x (0≤x≤0.3) alloys. The alloys, which crystallize in the L2₁ structure, were found to exhibit ferromagnetic behavior. The lattice constant a at room temperature decreases with increasing x, whereas the Curie temperature T_C decreases linearly. At 5 K the magnetic moment per formula unit first increases with increasing x and then saturates for x≥0.2. The experimental results are discussed in terms of the influence of the Mn-Mn exchange interactions between the Mn atoms on the Sn and Mn sites.     

Signatures of spin-glass freezing in Co/CoO nanospheres and nanodiscs

We present a study of the magnetic properties of Co nanoparticles having a combination of both spherical and disk shapes. The hcp Co nanospheres with an average diameter of 11 nm and nanodiscs of dimensions ∼2.5×15 nm² were prepared by thermal decomposition of di-cobalt octacarbonyl in the presence of an amine surfactant. The as-synthesized nanoparticles were oxidized to grow an antiferromagnetic layer. High resolution transmission electron microscopy showed the presence of a ferromagnet/antiferromagnet (Co/CoO) interface with a 2.2-nm thick CoO shell on the spherical nanoparticles and 0.5 nm thick on nanodiscs. We report the temperature and field dependent DC magnetization, frequency, field, and temperature dependent AC susceptibility, and the radio frequency transverse susceptibility. A low temperature paramagnetic behavior was observed in the DC magnetization at high fields and is assigned to defects in the CoO shell that are not coupled to the antiferromagnetic lattice. Our results support the existence of a low temperature frozen, disordered magnetic state, characterized by a strong exchange coupling between the structurally disordered, spin-glass CoO shell and Co core.     

Observation of the exchange spring behavior in hard-soft-ferrite nanocomposite

Nanocomposite of hard (BaFe₁₂O₁₉) and soft ferrite (Ni_0.8Zn_0.2Fe₂O₄) are prepared by the mixing of the individual ferrite components at appropriate ratio and subsequent heat treatment. Initially the microstructure of the individual phases is controlled by suitable processing. We have observed the exchange spring behavior in the soft-hard ferrite composite for the first time by tailoring the particle size of the individual phases and by suitable thermal treatment of the composite. It is found that the exchange interaction dominates over the dipolar interaction for smaller particle sizes of the soft ferrite. The magnetization of the composite showed hysteresis loop that is characteristic of the exchange spring system. This gives experimental proof for some theoretical modeling as well as paves way for developing magnet with higher (BH)_max product based on ferrites.     

Structural and magnetic studies on spark plasma sintered SmCo5/Fe bulk nanocomposite magnets

SmCo₅+x wt% Fe (x=0$x=0$, 5 and 10) nanocomposite powders were synthesized by mechanical milling and were consolidated into bulk shape by spark plasma sintering (SPS) technique. The evolution of structure and magnetic properties were systematically investigated in milled powders as well as in SPS samples. A maximum coercivity of 8.9 kOe was achieved in spark plasma sintered SmCo₅+5 wt% Fe sample. The exchange spring interaction between the hard and soft magnetic phases was evaluated using δM–H measurements and the analysis revealed that the SPS sample containing 5 wt% Fe had a stronger exchange coupling between the magnetic phases than that of the sample with10 wt% Fe.     

Quantum entanglement and quantum phase transitions in frustrated Majumdar-Ghosh model

By using the density matrix renormalization group technique, the quantum phase transitions in the frustrated Majumdar-Ghosh model are investigated. The behaviors of the conventional order parameter and the quantum entanglement entropy are analyzed in detail. The order parameter is found to peak at J₂∼0.58, but not at the Majumdar-Ghosh point (J₂=0.5). Although, the quantum entanglements calculated with different subsystems display dissimilarly, the extremes of their first derivatives approach to the same critical point. By finite size scaling, this quantum critical point J^C₂ converges to around 0.301 in the thermodynamic limit, which is consistent with those predicted previously by some authors (Tonegawa and Harada, 1987 [6]; Kuboki and Fukuyama, 1987 [7]; Chitra et al., 1995 [9]). Across the J^C₂, the system undergoes a quantum phase transition from a gapless spin-fluid phase to a gapped dimerized phase.     

The mean-size dependence of the exchange narrowing in molecular J-aggregates

The effect of segment-size fluctuations on exchange narrowing in a molecular J-aggregate of site-energy disordered distributions is studied using a one-dimensional Frenkel-exciton model. It is found that the segment-size disorder leads to the width of the absorption spectra deviating from the scaling law, σ^4/3 of the site-energy disordered standard deviation σ, being suitable for the system only with the site-energy disorder. In larger σ, the segment-size disorder has little influence on the linear absorption spectra. With increasing segment mean-length, the absorption line width monotonically increases, and then approaches a saturated value. By comparing a system of larger mean-length segment with a smaller one, both with the same segment-size disorder, it is found that the absorption line width of the former is broadened, and the exchange narrowing effect is reduced. The present result shows that the correlation effect can be partially maintained for the system with larger mean-length segment.     

Preparation and optical properties of soda-lime silicate glasses partially substituted by copper

The ion-exchange process was used to introduce copper ions into soda lime silicate glasses (SLS), the composition of which corresponds to the miscibility gape in the Na 2 O-SiO 2 system. The samples have been immersed either in a molten Cu 2 Cl 2 or CuCl 2 at various temperatures from the range 720-940 v K for different time. The observed green colour of glass is related with the 790-nm absorption band related to the cupric ions. The annealing either in air or in the hydrogen atmosphere was used for the reduction of copper. The effectiveness of these procedures was analysed on a basis of the penetration profiles monitored by roentgenographic methods (diffraction and EDAX). Transmission electron microscopy (TEM) observations of the replicated surface and common optical absorption measurements have been used to study the morphology of the dopant ions.     

Time-series analysis of foreign exchange rates using time-dependent pattern entropy

Time-dependent pattern entropy is a method that reduces variations to binary symbolic dynamics and considers the pattern of symbols in a sliding temporal window. We use this method to analyze the instability of daily variations in foreign exchange rates, in particular, the dollar–yen rate. The time-dependent pattern entropy of the dollar–yen rate was found to be high in the following periods: before and after the turning points of the yen from strong to weak or from weak to strong, and the period after the Lehman shock.