Crystal structures, phase relationships, and magnetic phase transitions of RsM4 compounds （R = rare earths, M = Si, Ge）

Our recent studies of the crystal structures, phase transitions, and magnetic properties of intermetallic compounds RsM4 （R = rare earths; M = Si, Ge） are reviewed briefly. First, crystal structures, phase relationships, and magnetic prop- erties of several 5：4 compounds, including Nd5 Si4-xGex, Pr5 Si4_xGex, Gds-xLaxGe4, La5 Si4, and Gd5 Sn4, are presented. In particular, the canted spin structures as well as the magnetic phase transitions in PrsSi2Ge2 and PrsGe4 investigated by neutron powder diffractions and small-angle neutron scattering are reviewed. Second, the crystal structures and magnetic properties of the most studied compounds Gds（Si,Ge）4 are summarized. The focus is on the parent compound GdsGe4, which is an amazing material exhibiting magnetic anisotropy, angular dependent spin-flop transition, metastable magnetic response, Griffiths-like phase, thermal effect under pulsed fields, antiferromagnetic and ferromagnetic resonances, pro- nounced effects of impurities, and high-field induced magnetic transitions.     

A Parallel Study on （BN）n and （HAlNH）n （n=11-22） Clusters： Geometry and Stability

A parallel study on （BN）n and （HAlNH）n （n = 11-22） clusters is presented herein with ab initio HF/6-31G^＊ method. Two types of structures, i.e. cage-like and needle-shaped, are constructed. The calculated results indicate that the classical cage-like geometry is energetically more favourable for （BN）n while the needle-shaped （HAlNH）n structures are more stable than their cage-like counterparts. It is suggested that the nanostructures with higher structural similarity to the corresponding bulk phases possess greater stability. This idea leads to the viable way to intercept segment from bulk materials to construct models for theoretical study of complex nanostructures.     

Phase Transition and Phonon Spectrum of Zinc-Blende Structure ZnX （X = S,Se, Te）

Calculations have been performed to investigate the pressure-induced solid-solid phase transitions and the mechanical stability for three zinc-blende II-VI semiconductor compounds： ZnS, ZnSe, ZnTe by ab initio plane-wave pseudopotential density functional theory （DFT）. Using the generalized gradient approximation （GGA） for exchange and correlation in the scheme of Perdew-Wang 1991 （P Wgl ）, the ground state properties and equation of state are obtained, which are well consistent with the experimental data available and other calculations. On the basis of the forth-order Birch-Murnaghan equation of states, the transition pressures Pt are determined through the analysis of enthalpy variation with pressure. A linear-response approach is used to calculate the frequencies of the phonon dispersion. Finally, by the calculations of phonon frequencies, some thermodynamic properties such as the vibrational contribution to the Helmholtz free energy （F）, enthedpy （H）, entropy （S）, and the heat capacity （Cv ） are also successfully obtained.     

Doping effects on structural and magnetic evolutions of orthoferrite SmFe（1-x） Alx O3

The structural and magnetic properties of SmFeO3 with B site substitution of non-magnetic atom A1 are investigated. The x-ray diffraction patterns show that SmFe（1-x）AlxO3 remains an orthorhombic structure within the whole doping range, and the unit-cell volume decreases monotonically with the increase of doped A1 concentration. Besides, the octa- hedral tilting distortions of FeO6 are found to be alleviated while the tolerance factor increases. However, the relationship between the lattice parameters and Al concentration is observed to deviate from Vegard＇s rule, and this may be caused by magnetostriction effects. For the doping content values in a range 0 〈 x 〈 0.6, the ferromagnetism, antiferromagnetism, and paramagnetism are observed to occur continuously. Moreover, the magnetization and the spin reorientation temperature （Tk） decrease monotonically as Al content value increases. With the doping content values being x = 0.8 and 1.0, these compounds only show paramagnetic behavior.     

A density functional theory structures,stabilities, and study on size-dependent electronic properties of bimetallic MnAgm （M=Na,Li; n ＋ m ≤ 7） clusters

The equilibrium geometries, relative stabilities, and electronic properties of MnAgm（M=Na, Li; n ＋ m ≤ 7） as well as pure Agn, Nan, Lin （n ≤ 7） clusters are systematically investigated by means of the density functional theory. The optimized geometries reveal that for 2 ≤ n ≤ 7, there are significant similarities in geometry among pure Agn, Nan, and Lin clusters, and the transitions from planar to three-dimensional configurations occur at n = 7, 7, and 6, respectively. In contrast, the first three-dimensional （3D） structures are observed at n ＋ m = 5 for both NanAgm and LinAgm clusters. When n ＋ m ≥5, a striking feature is that the trigonal bipyramid becomes the main subunit of LinAgm. Furthermore, dramatic odd-even alternative behaviours are obtained in the fragmentation energies, secondorder difference energies, highest occupied and lowest unoccupied molecular orbital energy gaps, and chemical hardness for both pure and doped clusters. The analytic results exhibit that clusters with an even electronic configuration （2, 4, 6） possess the weakest chemical reactivity and more enhanced stability.     

High stability of the goldalloy fullerenes：A density functional theory investigation of M_（12）@Au_（20）（M=Na,Al,Ag,Sc,Y,La,Lu,and Au） clusters

Discovering highly stable metal fullerenes such as the celebrated C 60 is interesting in cluster science as they have potential applications as building blocks in new nanostructures.We here investigated the structural and electronic properties of the fullerenes M 12 @Au 20（M=Na,Al,Ag,Sc,Y,La,Lu,and Au）,using a first-principles investigation with the density functional theory.It is found that these compound clusters possess a similar cage structure to the icosahedral Au 32 fullerene.La 12 @Au 20 is found to be particularly stable among these clusters.The binding energy of La 12 @Au 20 is 3.43 eV per atom,1.05 eV larger than that in Au 32.The highest occupied molecular orbital-lowest unoccupied molecular orbital（HOMO-LUMO） gap of La 12 @Au 20 is only 0.31 eV,suggesting that it should be relatively chemically reactive.     

A novel strong green phosphor： K3Gd（PO4）2：Ce^3＋, Tb^3＋ for a UV-excited white light-emitting-diode

A series of K3Gd1-x-y（PO4）2：xCe^3＋, yTb^3＋ phosphors are synthesized by the solid-sate reaction method. X-ray diffraction and photoluminescence spectra are utilized to characterize the structures and luminescence properties of the as-synthesized phosphors. Co-doping of Ce^3＋ enhances the emission intensity of Tb^3＋ greatly through an efficient energy transfer process from Ce^3＋ to Tb^3＋. The energy transfer is confirmed by photoluminescence spectra and decay time curves analysis. The efficiency and mechanism of energy transfer are investigated carefully. Moreover, due to the non- concentration quenching property of K3Tb（PO4）2, the photoluminescence spectra of K3Tb1-x（PO4）2：xCe^3＋ are studied and the results show that when x = 0.11 the strongest Tb^3＋ green emission can be realized.     

Influence of rotational excitation and collision energy on the stereo dynamics of the reaction： N（4S）＋H2 （v = 0, j = 0, 2, 5, 10） →NH（X3∑-）＋H

The N+H₂ reaction has attracted a great deal of attention from both the experimental and the theoretical community, and most of the attention has been paid to the first excited state N(²D) atoms in collisions with hydrogen molecules and the scalar properties of the reaction. In this paper, we study the stereo dynamical properties and calculate the reaction cross sections of the N(⁴S) + H₂ (v=0, j=0, 2, 5, 10) → NH(X³Σ^-) + H using the quasi-classical trajectory (QCT) method on an accurate NH₂ potential energy surface (PES) reported by Poveda and Varandas [Poveda L A and Varandas A J C 2005 Phys. Chem. Chem. Phys. 7 2867], in a collision energy range of 25 kcal·mol^-1-140 kcal·mol^-1. Results indicate that the reactant rotational excitation and initial collision energy both have a considerable influence on the distributions of the k-j′ correlation, the k-k′-j′ correlation and k-k′ correlation. The differential cross section is found to be sensitive to collision energy.     

Effects of A1 site occupation on dielectric and ferroelectric properties of Sr4CaRTi3Nb7O30（R=Ce,Eu） tungsten bronze ceramics

Sr4Ca RTi3Nb7O30（R = Ce, Eu） tungsten bronze ceramics are prepared by a standard solid state reaction method. The effects of A1 site occupation on the dielectric and ferroelectric properties of Sr4 Ca RTi3Nb7O30（R = Ce, Eu） tetragonal tungsten bronzes are investigated. The Sr4 Ca Ce Ti3Nb7O30 shows a normal transition behavior due to the closer size ion occupation in A1 sites, which could suppress the distortion of B2 octahedra effectively. Sr4 Ca Eu Ti3Nb7O30 ceramic exhibits two dielectric anomalies, which might be related to the fact that the large radius difference between Ca^2＋ and Eu^3＋ could lead to the uneven distribution of Ca^2＋ and Eu^3＋ in A1 sites and form two slightly different kinds of compositions with different transition temperatures in the structure. Our results indicate that the ionic radius difference in A1 sites plays an important role in determining the dielectric and ferroelectric natures of the filled tungsten bronze ceramics. Polarization–electric field（P–E） curves are evaluated at room temperature and both of them show hysteresis loops. Sr4 Ca Ce Ti3Nb7O30 shows a fat hysteresis loop, indicating the long-range ferroelectric order in the ceramic. The current density–electric field（J–E） curves are measured at room temperature with a largest leakage current density of ～ 10^-6A/cm^2, indicating that their leakage currents are rather low.