Phase transition and high pressure behavior of Zirconium and Niobium carbides

We have predicted the phase transition pressure (P _T )and high pressure behavior of Zirconium and Niobium carbide (ZrC, NbC). The high pressure structural phase transitions in ZrC and NbC has been studied by using a two body inter-ionic potential model, which includes the Coulomb screening effect, due to the semi-metallic nature of these compounds. These transition metal carbides have been found to undergo NaCl (B1) to CsCl (B2)-type structural phase transition, at high pressure like other binary systems. We predict such structural transformation in ZrC and NbC at a pressure of 98GPa and 85GPa respectively. We have also predicted second order elastic constant and bulk modulus. The present theoretical work has been compared with the corresponding experimental data and prediction of LAPW and GGA and LDA theories.      

High pressure behavior and structural properties of transition metal carbides

A pressure induced structural phase transition from NaCl-type (B₁) to CsCl-type (B₂) structure has been predicted in transition metal carbides, namely TiC, ZrC, NbC, HfC, and TaC by using an interionic potential theory with modified ionic charge (Z_m ), which includes Coulomb screening effect due to d-electron. The phase transition pressure (P_T ) relies on large volume discontinuity in pressure–volume relationship, and identifies the structural phase transition from B₁ phase to B₂ phase. The variation of second-order elastic constants with pressure follows a systematic trend identical to that observed in other compounds of NaCl-type structure. The Born criterion for stability is found to be valid in transition metal carbides.     

Pressure induced phase transition in rare earth mono-antimonides

Pressure induced structural phase transition of mono-antimonides of lanthanum, cerium, praseodymium and neodymium (LnSb, Ln=La, Ce, Pr and Nd) has been studied theoretically using an inter-ionic potential with modified ionic charge which parametrically includes the effect of Coulomb screening by the delocalized f electrons of rare earth (RE) ion. The anomalous structural properties of these compounds have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Ln ion with the p orbital of neighbouring antimonide ion. All the four compounds are found to undergo from their initial NaCl (B₁) phase to body centered tetragonal (BCT) phase at high pressure and agree well with the experimental results. The body centered tetragonal phase is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82. The transition pressure of LnSb compounds is observed to increase with decreasing lattice constant in NaCl phase. The nature of bonds between the ions is predicted by simulating the ion-ion (Ln-Ln and Ln-Sb) distances at high pressure. The calculated values of elastic constants are also reported.     

High-pressure behaviour and elastic properties of heavy rare-earth Gd monopnictides

Pressure-induced structural phase transition of gadolinium monopnictides GdX (X=As and Sb) has been studied theoretically using an inter-ionic potential theory. This method has been found quite satisfactory in case of the pnictides of rare-earth and describes the crystal properties in the framework of rigid-ion model. We have modified the ionic charge so that it may include the Coulomb-screening effect by the delocalization of f electron of the rare-earth ion. The anomalous structural properties of these compounds with many f electrons have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Gd ion with the p orbital of neighbouring pnictogen ion. Both the compounds are found to undergo from their initial NaCl (B₁) structure to body centered tetragonal (BCT) structure at high pressure and agree well with the experimental results. The BCT structure is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82–0.85. The nature of bonds between the ions is predicted by simulating the ion–ion (Gd–Gd and Gd–X) distance at high pressure. Elastic properties of these compounds have also been studied with their second-order elastic constants.     

High pressure behavior of alkaline earth tellurides

We have predicted high pressure structural behavior and elastic properties of alkaline earth tellurides (AETe; AE = Ca, Sr, Ba) by using two body interionic potential approach with modified ionic charge (Z _m e). This method has been found quite satisfactory in case of the rare earth compounds. The equation of state curve, structural phase transition pressure from NaCl (B1) to CsCl (B2) phase and associated volume collapse at transition pressure of alkaline earth tellurides (AETe) obtained from this approach, so have been compared with experimentally measured data reveal good agreement. We have also investigated bulk modulus, second and third order elastic constants and pressure derivatives of second order elastic constants at ambient pressure which shows predominantly ionic nature of these compounds. First time, we have calculated the Poisson ratio, Young and Shear modulus of these compounds.      

High pressure effect on structural and mechanical properties of some LnO (Ln=Sm, Eu, Yb) compounds

The structural and mechanical properties of LnO (Ln=Sm, Eu, Yb) compounds have been investigated using a modified interionic potential theory, which includes the effect of Coulomb screening. We predicted a structural phase transition from NaCl (B₁)- to CsCl (B₂)-type structure and elastic properties in LnO compounds at very high pressure. The anomalous properties of these compounds have been correlated in terms of the hybridisation of f-electrons of the rare earth ion with conduction band and strong mixing of f-states of lanthanides with the p-orbital of neighbouring chalcogen ion. For EuO, the calculated transition pressure, bulk modulus and lattice parameter are close to the experimental data. The nature of bonds between the ions is predicted by simulating the ion-ion (Ln-Ln and Ln-O) distances at high pressure. The second order elastic constants along with shear modulus and Young's modulus, elastic anisotropy and Poisson's ratio are also presented for these oxides.     

Structural,mechanical and thermal properties of some Holmium Pnictides under pressure: A theoretical approach

The high pressure structural, elastic and thermal properties of holmium pnictides HoX (X=N, P, As and Bi) were investigated theoretically by using an inter-ionic potential theory with modified ionic charge parameter. We have predicted a structural phase transition from NaCl (B₁) to CsCl (B₂)-type structure at pressure of 139 GPa for HoN, 52 GPa for HoP, 44 GPa for HoAs and 26 GPa for HoBi. Other properties, such as lattice constant, bulk modulus, cohesive energy, second and third-order elastic constants were calculated and compared with the available experimental and theoretical data. In order to gain further information the brittle behaviour of these compounds was observed. Some other properties like Shear modulus (G), Young's modulus (E), Poisson's ratio (ν), anisotropy factor (A), sound velocities, Debye temperature (θ_D) were calculated. The variation of elastic constants (C₁₁ and C₄₄) and Debye temperature (θ_D) with pressure was also presented.     

Pressure-induced structural phase transition and electronic properties of RESb (RE = Ho,Er and Tm) compounds: ab initio calculations

The structural phase transition and electronic properties at ambient (B ₁-phase) and high pressure (B ₂-phase) of heavy rare earth monoantimonides (RESb; RE?=?Ho, Er, and Tm) have been studied theoretically using the self-consistent tight binding linear muffin tin orbital method. These compounds show metallic behavior under ambient condition and undergo a structural phase transition to the B ₂ phase at high pressure. We predict a structural phase transition from the B ₁ to B ₂ phase in the pressure range 30.0–35.0?GPa. Apart from this, the ground state properties, such as lattice parameter and bulk modulus are calculated and compared with the available theoretical and experimental results.     

Structural, high pressure and elastic properties of transition metal monocarbides: A FP-LAPW study

The structural, elastic and thermal properties of four transition metal monocarbides ScC, YC (group III), VC and NbC (group V) have been investigated using full potential linearized augmented plane wave (FP-LAPW) method within generalized gradient approximation (GGA) both at ambient and high pressure. We predict a B₁ to B₂ structural phase transition at 127.8 and 80.4 GPa for ScC and YC along with the volume collapse percentage of 7.6 and 8.4%, respectively. No phase transition is observed in case of VC and NbC up to pressure 400 and 360 GPa, respectively. The ground state properties such as equilibrium lattice constant (a₀), bulk modulus (B) and its pressure derivative (B′) are determined and compared with available data. We have computed the elastic moduli and Debye temperature and report their variation as a function of pressure.     

Structural phase transitions of the B1–B2 type in small-sized ionic crystals

The features of structural phase transitions that occur under high pressure are studied. The density functional theory is used to calculate the B1–B2 phase transition pressure as a function of the crystal size for small-sized alkali halide crystals. A size effect (an increase in the phase transition pressure as the crystal grain radius decreases) is revealed for the B1–B2 transitions in all halogen compounds except for lithium fluoride, for which the dependence is inverse.     

Pressure-induced structural phase transition in RbAu

Using the first principle method based on density functional theory, the structural and elastic properties calculations of RbAu have been performed. The results demonstrate that RbAu is stable in the CsCl structure (B2) at ambient pressure, which is in well agreement with the experimental results. And there exists a structural phase transition from CsCl-type structure (B2) to NaTi-type structure (B32) at the transition pressure of approximate 6 GPa. The pressure effects on the elastic properties are discussed and the elastic property calculation indicates elastic instability maybe provide phase transition driving force according to the variations relation of the elastic constant versus pressure.     

The high-pressure structural transition in MnS: an ab initio study

The structural phase transition between B1 (α-MnS) and B3 (β-MnS) is investigated using a density functional theory method. The structural phase transition pressure Pt from α-MnS to β-MnS, which is determined on the basis of the third-order Birch–Murnaghan equation of states, is 30.75?GPa. Also, the lattice parameters a, the bulk modulus B and pressure derivative of bulk modulus B′, which are generally in good agreement with experiments and other theoretical values, are obtained under zero pressure. For further investigation of the structural phase transition pressure of MnS, the relative volumes V/V ₀, the bulk modulus B, first and second pressure derivatives (B′ and B″) of bulk modulus for the two structures of MnS have been calculated under various pressures.     

Analysis of structural properties of refractory compounds at high temperature and pressure using a potential model

In this paper we focused on the structural and elastic properties of four transition metal mononitrides (TMNs) (M=Ti, Nb, Hf and Zr) by using realistic three body interaction potential (RTBIP) model, including the role of temperature. These TMN compounds have been found to undergo NaCl (B1) to CsCl (B2) phase transition, at a pressure quite high as compared to other binary systems. We successfully obtained the phase transition pressures and volume changes at different temperatures. In addition, elastic constants of TMNs at different temperatures are discussed. The present theoretical results have been compared with the available experimental data and predictions of LDA theory.     

Bond-stretching and bond-bending force constant of binary tetrahedral (AB and AB) semiconductors

In this Letter we present the two expressions relating the bond-stretching force constant (α in N/m) and bond-bending force constant (β in N/m) for the A^IIIB^V and A^IIB^VI semiconductors with the product of ionic charges (Z₁Z₂) and nearest neighbor distance d (Å). Interatomic force constants of these compounds exhibit a linear relationship when plotted on a log-log scale against the nearest neighbor distance d (Å), but fall on different straight lines according to the ionic charge product of the compounds. A fairly good agreement has been found between the observed and calculated values of the α and β for binary tetrahedral semiconductors.     

Phase transformation and elastic behavior of MgX (X=S, Se, Te) alkaline earth chalcogenides

Pressure induced structural aspects of NaCl-type (B1) to CsCl-type (B2) structure in alkaline earth chalcogenides (AECs) magnesium chalcogenides (MgX; X=S, Se, and Te) are presented. An effective interionic interaction potential (EIoIP) with long-range Coulomb interactions and the Hafemeister and Flygare type short-range overlap repulsion extending up to the second neighbor ions and the van der Waals (vdW) interaction is developed. The vdW coefficients are evaluated following the Slater-Kirkwood variational method, as both the ions are polarizable. The present calculations have revealed reasonably good agreement with the available experimental data on structural transition (B1-B2 structure), the phase transition pressures P_t of 167 (MgS), 170 (MgSe), and 176 (MgTe) GPa as well the elastic properties. The calculated values of the volume collapses [ΔV(P)/V(0)] are also closer to their observed data. Further, the variations of the second and third order elastic constants with pressure have followed a systematic trend, which are almost identical to those exhibited by the observed data measured for other semiconducting compounds with rocksalt (B1) type crystal structure. The Born and relative stability criteria is valid in Mg monochalcogenides.     

Chemical shifts of the LIII absorption discontinuity of rhenium

Chemical shifts of the X-ray L_III absorption discontinuities of rhenium in some of its binary and ternary compounds have been studied using a bent crystal X-ray spectrograph. The chemical shifts (ΔE) are found to be governed by the effective charges (q) on the absorbing ions, which have been calculated using Suchet's theory. For the compound ReCl₅, however, the effective ionic charge cannot be calculated since the pentavalent radius of rhenium is not known. The ΔE, q plot has been used to determine the charges on the rhenium ions in ReCl₅ as well as in two ternary compounds KReO₄ and NaReO₄. Our work has enabled us to determine the ionic radius of pentavalent rhenium.     

Features of the semiconductor-metal transition in GaAs at ultrahigh pressures: New intermediate phases

Using the thermopower method (Seebeck effect), the semiconductor-metal transition that occurs in gallium arsenide single crystals of n and p types at ultrahigh pressures P above ～11–18 GPa has been studied. It has been found that the transition in n-type samples begins at lower pressures. In the region of the semiconductor-metal phase transition, features have been observed on the thermopower dependences S(P). These features indicate that lattices intermediate between the initial semiconductor structure of zinc blende and the Cmcm high-pressure orthorhombic metallic phase are formed. By analogy with ZnTe, one intermediate phase (semiconductor with hole conductivity) is suggested to have the cinnabar structure and the second intermediate phase (semimetallic with electron conductivity) possibly has the SC16 structure. A model of the semiconductor-metal transition is discussed. The behavior of the thermoelectric properties in GaAs under pressure is compared with the behavior of these properties in other A_NB_8?N semiconductors, which also undergo the transition to the metallic state.     

First principles study of structural,electronic, mechanical and thermal properties of A15 intermetallic compounds Ti3X (X=Au,Pt, Ir)

The structural, electronic, elastic, mechanical and thermal properties of Ti₃Au, Ti₃Pt and Ti₃Ir intermetallic compounds crystallizing in A15 structure have been studied using density functional theory within generalized gradient approximation (GGA) for the exchange correlation potential. Elastic properties such as Young's modulus (E), rigidity modulus (G), bulk modulus (B), Poisson's ratio (σ) and elastic anisotropic factor (A) have been calculated. From the present study it is noted that Ti₃Ir is the hardest compound among the three materials studied due to its larger bulk modulus. Also, it is more ductile in nature.