Effect of exchange-coupling interaction on anisotropy of grain in nanoscaled magnets

The effect of inter-grain exchange-coupling interaction on the anisotropy of grain in nanoscaled magnets has been investigated by putting forward an expression of anisotropy at grain boundary, , which is suitable for different coupling conditions, and expresses well the coherency between soft and hard grains. The average anisotropy of grain 〈K^ij〉 has been calculated based on and the theory of partial exchange-coupling interaction. It has been found that the average anisotropy of hard or soft grain, 〈K^hh〉 or 〈K^ss〉, increases with increasing grain size D monotonously when hard-hard or soft-soft grains couple. When soft-hard grains touch each other, with increasing D, the variation of average anisotropy of soft-hard grain 〈K〉 depends on the anisotropy at grain interface , which denotes the affection degree of hard grain on the anisotropy of soft grain. Compared with other results, it is more reasonable that ranges from to . The variations of anisotropy with D we calculated are consistent with those of coercivities given by other authors when is fixed in a certain range.     

A theoretical study of BrCN in the Π electronic ground state: Large amplitude bending motion

We have calculated the three-dimensional potential energy surfaces for the 1 ²A′ and 1 ²A″ states of BrCN⁺ at the MR-SDCI_DK+Q/[QZP-ANO-RCC (Br, C, N)] level of theory, where MR-SDCI_DK means ‘multi-reference single and double excitation configuration interaction calculation with Douglas-Kroll Hamiltonian.’ These ab initio potential energy surfaces have a common minimum (corresponding to the state) at a linear equilibrium structure with r_e(Br-C) = 1.735 Å and r_e(C-N) = 1.199 Å. Variational RENNER calculations yield a zero-point averaged structure (with the structural parameters calculated as expectation values over rovibrational wavefunctions) with 〈r(Br-C)〉₀ = 1.739 Å, 〈r(C-N)〉₀ = 1.204 Å, and 〈∠(Br-C-N)〉₀ = 172(4)°. A severe Fermi resonance between 2ν₂ and ν₃ has been found theoretically for the ²A″ potential energy surface. Comparing the ab initio zero-point averaged structure with a recent, experimentally derived r₀ structure, it is concluded that the effects of large-amplitude bending motion should be taken into account explicitly in the process of deriving the r₀ structure from the experimental values of the rotational constants. The electronic structure of BrCN⁺ has also been discussed.     

Anisotropy analysis of the surface stress and surface energy in Cu surfaces with the modified embedded atom method

Taking Cu as an example, the surface stress and surface energy in three low index surfaces and two families of representative surfaces and belong to [0 0 1]- and -rotating axis respectively, have been calculated using MEAM. For the three low index surfaces, the decrease in the surface energy is small after relaxation, while the surface stresses in the surface planes τ_xx and τ_yy show opposite changes (decreasing and increasing) for inward and outward relaxations. The resulting relaxation direction is related to the normal stress τ_zz before relaxation. For the surfaces of the and families, with the increasing angle α (between the and (1 0 0) planes, and between and (0 0 1) planes, respectively), the surface stress and surface energy go through an oscillatory change. The surface stress and surface energy are symmetric about the planes (1 0 0), (1 1 0) and (0 1 0) at α=0^°, 45^° and 90^°, and about the planes (0 0 1) and (1 1 0) at α=0^° and 90^° respectively, due to crystal symmetry.     

Free energies of steps on (111) fcc surfaces

For a hexagonal two-dimensional lattice we derive, using a surprisingly simple route, exact expressions for the step free energies along the high symmetry directions, 〈1-10〉 and 〈11-2〉. If we consider only nearest-neighbor interactions, ε, and ignore step overhangs the step free energy vanishes at a temperature . In a more sophisticated model that incorporates step overhangs we find a reduction of T_R to about 0.87ε/k_b. The obtained step free energy expressions are also valid for the free energy of walls between two regions of opposite spins of the triangular 2D Ising system.     

Origin of photoluminescence in nanocrystalline Si:H films

We have studied the origin of photoluminescence (PL) from hydrogenated nanocrystalline silicon (nc-Si:H) films produced by a plasma-enhanced chemical vapor deposition technique using SiF₄/SiH₄/H₂ gas mixtures. The nc-Si:H films were characterized using X-ray diffraction, infrared, Raman spectroscopy, optical absorption and stress, and were examined for PL by varying the deposition temperature (T_d) under two different hydrogen flow rate ([H₂]) conditions. The PL exhibited two peaks at around 1.7-1.75 and 2.2-2.3 eV. The peak energy, E_PL, of the 1.7-1.75-eV PL band was found to shift as T_d or [H₂] changes. It was found that the decrease in T_d acts to decrease the average grain size, 〈δ〉, and to increase both the optical band gap, , and the E_PL values. By contrast, the increase in [H₂] decreased the 〈δ〉 value, while increased the values of and E_PL. Thus, as either T_d decreases or [H₂] increases, it is found that a decrease in 〈δ〉 corresponds well with increases in and E_PL. As a consequence, it was suggested that an increase in E_PL of the 1.7-1.75-eV PL band can be connected with an increase in , through a decrease in 〈δ〉. However, the PL process cannot be connected with the transition between both the bands, related to formation of nanocrystals. Based on these results, it was proposed that the use of both low T_d and high [H₂] conditions would allow to grow nc-Si:H films with small grains.     

Excluded volume effect on entropy and clustering behaviors in supercooled liquids and glasses

We study the significant entropy changes in supercooling and glass transition by developing a two (H and L) state cluster model, where the H-state represents the clusters with the coordination number z being larger than the reference size z_R and the L-state those with z<z_R, respectively. We exploit the excluded volume effect on the clustering behaviors of various glass-formers and the temperature dependence (at fixed pressure of 1 atmosphere) of the entropy difference between the two cluster states on the basis of , where as taken universally for all the glass-formers investigated. The temperature dependence of the average size 〈z_c^∗〉 of clusters with z≥z_R is then determined for some representative glass-formers, such as GeO₂, 1-propanol, glycerol, propylene carbonate, o-terphenyl, and so forth, covering the entire fragility spectrum studied experimentally. As a result, the temperature dependence of 〈z_c^∗〉 is found to highly depend on the fragility index ? associated with the temperature dependence of the excluded volume B^∗(?,T) of which statistical mechanical representation is given by the generic van der Waals equation of state. With decreasing T toward the glass transition temperature T_g, 〈z_c^∗〉 increases to attain universally about 13 at T_g regardless of the fragility and molecular details of the glass-formers. We specifically analyze in depth the theoretical predictions for the cluster sizes and the experimental estimations for the length scales associated with temporary clusters of slow segments in supercooled glycerol as about 1.4±0.5 nm for glycerol at 10 K above T_g. Given the large uncertainties associated with the experiment, the present theory appears to be in good agreement with the experiment.     

Anisotropy of the magnetocaloric effect in DyNiAl

We present study of the anisotropic magnetocaloric effect in DyNiAl. This compound crystallizes in the hexagonal ZrNiAl-type structure, orders magnetically below and undergoes a further magnetic phase transition at . The Dy-moments are aligned ferromagnetically along the hexagonal c-axis below T_C, the additional antiferromagnetic component develops within the basal plane below T₁. The magnetocaloric effect was evaluated from the magnetization measurements with field applied along the c-axis and perpendicular to it. Our data reveal a strong anisotropy of the magnetocaloric effect. The large effect occurs for field applied along the c-axis whereas the entropy change is small for the perpendicular field direction.     

Sapphire (0 0 0 1) surface modifications induced by long-pulse 1054 nm laser irradiation

We have investigated modifications of sapphire (0 0 0 1) surface with and without coating, induced by a single laser pulse with a 1054 nm wavelength, 2.2 s duration, 7.75 mm spot and energy of 20-110 J. A holographic optical element was used for smoothing the drive beam spatially, but it induced small hotspots which initiated damage on the uncoated and coated surfaces. The individual damage effects of hotspots became less pronounced at high fluences. Due to high temperature and elevated non-hydrostatic stresses upon laser irradiation, damage occurred as fracture, spallation, basal and rhombohedral twinning, melting, vitrification, the formation of nanocrystalline phases, and solid-solid phase transition. The extent of damage increased with laser fluences. The formation of regular linear patterns with three-fold symmetry ( directions) upon fracture was due to rhombohedral twinning. Nanocrystalline -Al₂O₃ formed possibly from vapor deposition on the coated surface and manifested linear, triangular and spiral growth patterns. Glass and minor amounts of -Al₂O₃ also formed from rapid quenching of the melt on this side. The - to -Al₂O₃ transition was observed on the uncoated surface in some partially spalled alumina, presumably caused by shearing. The nominal threshold for laser-induced damage is about 47 J cm⁻² for these laser pulses, and it is about 94 J cm⁻² at the hotspots.     

Random walks and diameter of finite scale-free networks

Dynamical scalings for the end-to-end distance R_ee and the number of distinct visited nodes N_v of random walks (RWs) on finite scale-free networks (SFNs) are studied numerically. 〈R_ee〉 shows the dynamical scaling behavior , where is the average minimum distance between all possible pairs of nodes in the network, N is the number of nodes, γ is the degree exponent of the SFN and t is the step number of RWs. Especially, in the limit t→∞ satisfies the relation , where d is the diameter of network with for γ≥3 or for γ<3. Based on the scaling relation 〈R_ee〉, we also find that the scaling behavior of the diameter of networks can be measured very efficiently by using RWs.     

Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia

A Ti-rich oxide, (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)_∑=1.0O_1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3¯m and unit-cell parameters a=4.8830(5) Å and V=116.43(4) Å³. Like stabilized cubic zirconia, the structure of (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 is also relaxed, with all O atoms displaced from the (, , ) position along 〈1 0 0〉 by 0.319 Å and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 Å. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K₀=164(4) GPa, K′=4.3(7), and V₀=116.38(3) Å³. The bulk modulus of (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO₂ or that (~210 GPa) estimated for cubic ZrO₂. This study demonstrates that cubic TiO₂ may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 has the greatest ratio of Ti⁴⁺ content vs. vacant O²⁻ sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.     

Vibronic transition moments and line intensities for H2O

Ab initio calculations of the electronic dipole moment components for the and electronic states and the electronic transition moment for the - transition of H₂O⁺ have been carried out. Parameterized analytical functions have been fitted through the computed ab initio data points, and the resulting dipole moment and transition moment surfaces have been used, along with potential energy surfaces derived from the ab initio results of Brommer et al. [J. Chem. Phys. 98 (1993) 5222], to simulate H₂O⁺ spectra and to generate an extensive set of vibronic transition moments for the and band systems of H₂O⁺. The work is made with the dual purpose of facilitating further assignments of high-resolution spectra [J. Mol. Spectrosc. 219 (2003) 258] and of allowing cometary spectra of H₂O⁺ to be simulated [Ap. J. 574 (2002) L183].     

The luminescence of Sm in alkaline earth borophosphates

The temperature-dependent luminescence of Sm²⁺ ions in MBPO₅ was studied. At low temperature, Sm²⁺ in this series shows 4f⁶→4f⁶ luminescence with only a single emission line observed for the transition, revealing that only one crystallographic cationic site is available for Sm²⁺ in all the hosts. With increasing temperature, the emission intensity of the transition increases whereas that of the transitions decreases. The transitions of Sm²⁺ were observed in BaBPO₅ and its intensity increases with increasing temperature. At , a broad band of the 4f⁵5d→4f⁶ luminescent transition of Sm²⁺ in SrBPO₅ and BaBPO₅ with maximum at appears due to the thermal population. The lifetime of the transition was recorded at different temperatures, showing a single exponential decay for Sm²⁺ in SrBPO₅ and BaBPO₅ but a non-single-exponential decay in CaBPO₅.     

Sub-Doppler high-resolution excitation spectroscopy of the S1 ← S0 transition of dibenzofuran

Rotationally resolved ultrahigh-resolution fluorescence excitation spectra of the S₁ ← S₀ transition of dibenzofuran have been observed using the technique of crossing a collimated molecular beam and the single-mode UV laser beam. 3291 rotational lines of the band and 3047 rotational lines of the band have been assigned. The band has been found to be a b-type transition, in which the transition moment is along the twofold symmetry axis of this molecule, and only the ΔK_a = ± 1 transitions were observed. The excited state is identified to be the S₁¹A₁(ππ^∗) state. In contrast with this, the band has been found to be an a-type transition in which the transition moment is along the long axis in plane. It indicates that the intensity of this vibronic band arises from vibronic coupling with the S₂¹B₂(ππ^∗) state. We determined the accurate rotational constants and the molecule have been shown to be planar both in the ground and excited states.