Crystal field effect and geometric frustration in Er2Ti2O7 —an XY antiferromagnetic pyrochlore

Magnetic susceptibility of powder Er₂Ti₂O₇ (ErT) is measured between 300 K and 80 K. shows a Curie-Weiss (CW) type behaviour with   ErTiO_3.5 and . A crystal field (CF) analysis of our experimental data, g-values (g_∥=0.27 and g_⊥=7.8) and the positions of two CF levels (reported earlier from an inelastic neutron scattering study) provide CF parameters and CF levels of the ground ⁴I_15/2 and excited multiplets of ErT. The theoretical follows a CW-type behaviour, with . Single-ion magnetic anisotropy (χ_⊥−χ_∥) is 9500×10⁻⁶ emu/mol ErTiO_3.5 at 300 K, which increases by ∼54 times at 10 K and ErT resembles an XY planar system. It can be inferred from CF analysis that the earlier observed change of from −13 K to −22 K below 50 K is not due to the CF effect. Nuclear hyperfine (HF) levels of ¹⁶⁷ErT and ¹⁶⁶ErT are calculated and the theoretical curve of vs. T (K) for T<T_N matches the observed results. Mössbauer lines expected for ¹⁶⁶ErT are also predicted.     

4-benzyl pyridinium dihydrogenmonophosphate C6H5CH2C5H4NHH2PO4 : Single-crystal structure and its conductivity in polycrystalline form

The salt 4-benzyl pyridinium dihydrogenmonophosphate is monoclinic P2₁/c with the following unit cell dimensions: ; ; ; and β=97.328(11). Also, , D_x=1.403, , F(000)=560; ; and R=0.0495 and R_w=0.0964 for 3733 independent reflections. The structure consists of infinite parallel two-dimensional planes built of H₂PO₄⁻ anions and C₆H₅CH₂C₅H₄NH⁺ cations mutually connected by strong O-H ?O and N-H ?O hydrogen bonding. There are no contacts other than the normal Van der Waals interactions between the layers. The conductivity relaxation parameters associated with some H⁺ conduction have been determined from an analysis of the spectrum measured in a wide temperature range.     

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.     

Relaxor behavior of K0.5La0.5Bi2Ta2O9 ceramics

Potassium lanthanum bismuth tantalate (K_0.5La_0.5Bi₂Ta₂O₉), a new relaxor ferroelectric was synthesized via the solid-state reaction route. X-ray structural studies along with Rietveld refinement confirmed it to be an n=2 member of the Aurivillius family of oxides and the refined lattice parameters are , and . The appearance of 1/2{h00} and 1/2{hk0} type superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak associated with frequency dependent dielectric maximum temperature was observed. The value of the diffuseness parameter γ=1.93, obtained from the fit of a modified Curie-Weiss law established the relaxor nature of the title compound. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein and . The relaxor behavior was attributed to the local polar ordering on A-sites.     

Near-infrared diode laser spectroscopy of the HCSi radical

The , , and band spectra of HCSi radical were investigated by means of near-infrared diode laser spectroscopy to determine precise molecular constants for the and states. The detailed analysis of the rotationally resolved band spectra, studied for the first time in the present investigation, leads to the precise determination of molecular constants for the state associated with the Renner-Teller interaction. We obtained −0.15126663(53) and 495.00698(30) cm⁻¹ as the Renner-Teller parameter ε and the bending vibrational frequency ω₂, respectively. Based on the molecular constants for the and states, the rotational levels of the state were analyzed to obtain molecular constants and information on upper state perturbations. Using the available spectroscopic data, valence force fields for both the and states were estimated to aid in understanding the vibrational energy levels of the HCSi radical.     

Theoretical study of local lattice structure of Mn in perovskite fluorides A2MF4 (A=K, Rb; M=Mg, Zn, Cd) series

A theoretical method for investigating the inter-relation between the molecular structure and electronic structure has been established on the basis of the 252×252 complete energy matrices for a 3d⁵ configuration ion in a tetragonal ligand field. By means of this method, which is independent of the X-ray diffraction, the local structure of the paramagnetic Mn²⁺ ion in perovskite fluorides A₂MF₄ (A=K, Rb; M=Zn, Mg, Cd) are determined directly by analyzing the EPR spectrum of octahedral Mn²⁺ center in A₂MF₄ crystals and the optical absorption spectrum of the (MnF₆)⁴⁻ cluster. It is shown that, comparing with the octahedral cubic structure, the local micro-structure in the vicinity of Mn²⁺ displays an elongated distortion when and a compressed distortion when , and ΔR vs. as well as ΔR vs. in the distortion region is, respectively, approximately linear. Simultaneously, the theoretical zero-field-splitting parameters , and are in good agreement with the experimental values.     

Laser induced fluorescence spectroscopy of NdO

Laser induced fluorescence spectra of ¹⁴²NdO have been excited using both fixed frequency argon ion and tunable ring dye lasers and detected at high resolution with a Fourier transform spectrometer. Nine low lying electronic states resulting from the Nd²⁺(4f³6s)O²⁻ configuration were detected of which four, the second lowest , 3, and 5 states, (2)2, (2)3, (2)5, and the lowest state, (1)6, have been observed for the first time. In addition, new vibrational levels were observed in the lowest , (1)5 (v=1) and second lowest , (2)4 (v=1, 2) states. Abnormally large Ω doubling in both states has been attributed to interactions involving neighboring and 0 states. Several perturbations were observed and used as an aid in assigning some of the states. Both the order and energies of the low lying states have been shown to be consistent with Ligand Field theory calculations. Rotational relaxation in several of the spectra has allowed calculation of accurate rotational constants for several states while, for other states, approximate parameters have been calculated from combination differences.     

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.     

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.