Compton scattering study and electronic properties of vanadium carbide: A validation of hybrid functional

In this paper, we have reported the isotropic Compton profile of VC measured using high energy (661.65 keV) γ-radiations from a ¹³⁷Cs isotope. To compare the experimental momentum densities, we have also employed the linear combination of atomic orbitals (LCAO). In addition, energy bands, density of states and Fermi surface topology of VC have been computed using FP-LAPW and LCAO methods. It is seen that the LCAO with hybridization of density functional theory and Hartree-Fock (so called B3LYP) gives a better agreement with the present Compton profile experiment. This shows validation of an exact exchange part in hybrid density functional. On the basis of energy bands, we have discussed the microscopic origin for the anomalous behavior of hardness of VC. The relative nature of bonding in VC and NbC is also discussed in terms of valence charge densities and Mulliken′s population analysis. To establish the role of Compton profiles in computation of cohesive properties of refractory materials, we have also calculated for the first time the cohesive energy using the present experimental Compton profile and compared it with the existing data.     

Investigation of electronic properties of crystalline arsenic chalcogenides: Theory and experiment

The electronic structure of crystalline As₂S₃ and As₂Se₃ has been calculated in this paper. We present the energy bands, density of states (DOS) and the Compton profiles using the linear combination of atomic orbitals (LCAO) scheme based on the density functional theory (DFT). From the calculated total and partial density of states it is seen that the lone-pair p-states of sulphur/selenium contribute closest to the Fermi energy level. To interpret the theoretical data on the Compton line shape, we have measured the Compton profiles on a 100 mCi ²⁴¹Am spectrometer. It is seen that the density functional theory within generalised gradient approximation gives a slightly better agreement with the experimental momentum densities. The nature of chemical bonding in arsenic chalcogenides is studied using Mulliken's population analysis and the experimentally measured equal-valence-electron-density profiles; As₂S₃ is found to be more ionic compared to As₂Se₃.     

Electronic properties and Compton profiles of molybdenum dichalcogenides

We present the first ever experimental Compton profiles of molybdenum dichalcogenides (MoX₂; X=S and Te) using 20 Ci ¹³⁷Cs Compton spectrometer. To interpret our experimental data, we have computed the theoretical profiles, energy bands and density of states using linear combination of atomic orbitals method in the framework of density functional theory and its hybridisation with Hartree Fock. The energy bands and density of states using full potential linearised augmented plane wave method have also been computed. Both theories show the existence of the indirect band gap. In addition, the relative nature of bonding is explained in terms of equal-valence-electron-density profiles and valence band charge densities.     

Electronic, elastic, optical properties of rutile TiO2 under pressure: A DFT study

The electronic, elastic constants and optical properties of rutile TiO₂ have been investigated using first principle pseudopotential method within generalized gradient approximation (GGA) proposed by Perdew-Burke-Ernzerhof (PBE). The calculated volume, bulk modulus and pressure derivative of bulk modulus are in good agreement with previous experimental and computational results. An underestimated band gap (1.970 eV) along with the higher density of states and expanded energy bands around the fermi level is obtained. Calculated elastic constants satisfying the Born stability criteria suggest that rutile TiO₂ is mechanically stable under higher hydrostatic pressure. The acoustic wave speeds in [1 0 0], [0 1 0], [0 0 1], [1 1 0] and [45° to [1 0 0] and [0 0 1]] directions are predicted using the investigated elastic constants. The dielectric constant is identified with respect to electronic band structure and is utilized to derive the other optical properties like refractive index, energy loss function, reflectivity and absorption. The effect of hydrostatic pressure (0-70 GPa) is described for listed properties. Our investigated results are in good accord with the existing theoretical and experimental results.     

Electronic and optical properties of ceramic Sc2O3 and Y2O3: Compton spectroscopy and first principles calculations

We present the first-ever experimental Compton profiles (CPs) of Sc₂O₃ and Y₂O₃ using 740 GBq ¹³⁷Cs Compton spectrometer. The experimental momentum densities have been compared with the theoretical CPs computed using linear combination of atomic orbitals (LCAO) within density functional theory (DFT). Further, the energy bands, density of states (DOS) and Mulliken's population (MP) data have been calculated using LCAO method with different exchange and correlation approximations. In addition, the energy bands, DOS, valence charge density (VCD), dielectric function, absorption coefficient and refractive index have also been computed using full potential linearized augmented plane wave (FP-LAPW) method with revised functional of Perdew–Becke–Ernzerhof for solids (PBEsol) and modified Becke Johnson (mBJ) approximations. Both the ab-initio calculations predict wide band gaps in Sc₂O₃ and Y₂O₃. The band gaps deduced from FP-LAPW (with mBJ) are found to be close to available experimental data. The VCD and MP data show more ionic character of Sc₂O₃ than Y₂O₃. The ceramic properties of both the sesquioxides are explained in terms of their electronic and optical properties.     

Thermodynamic properties of OsB under high temperature and high pressure

The energy-volume curves of OsB have been obtained using the first-principles plane-wave ultrasoft-pseudopotential density functional theory (DFT) within the generalized gradient approximation (GGA) and local density approximation (LDA). Using the quasi-harmonic Debye model we first analyze the specific heat, the coefficients of thermal expansion as well as the thermodynamic Grüneisen parameter of OsB in a wide temperature range at high pressure. At temperature 300 K, the coefficients of thermal expansion α_V by LDA and GGA calculations are 1.67×10⁻⁵ 1/K and 2.01×10⁻⁵ 1/K, respectively. The specific heat of OsB at constant pressure (volume) is also calculated. Meanwhile, we find that the Debye temperature of OsB increases monotonically with increasing pressure. The present study leads to a better understanding of how the OsB materials respond to pressure and temperature.     

A first-principle study of half-metallic ferrimagnetism in the Ti2CoGa Heusler compound

Electronic structure calculations based on density functional (DFT) theory within the generalized gradient approximation (GGA) for the Ti₂CoGa Heusler compound have been performed using the self-consistent full-potential linearized augmented plane wave (FPLAPW) method. The electronic band structures and density of states of the Ti₂CoGa compound show that the spin-up electrons are metallic, but the spin-down bands have a gap of 0.5 eV, resulting in stable half-metallic ferrimagnetic behavior with a magnetic moment of 2μ_B.     

Dissociative chemisorption of H2 on Pt(1 1 1): isotope effect and effects of the rotational distribution and energy dispersion

Six-dimensional quantum dynamics calculations on dissociative scattering of H₂ and D₂ from Pt(1 1 1) are performed. The six-dimensional potential energy surface used was generated using density functional theory employing the generalized gradient approximation. The isotope effect, the effect of widening the rotational distribution on the dissociation probability and the effect of the energy dispersion are investigated, as they are possible reasons for a discrepancy between previous theoretical work and molecular beam experiments. It was found that these effects cannot explain the differences between the theoretical and experimental results.     

Half-metallicity in the full-Heusler Co2ScP compound: A density functional study

The electronic structure and magnetic properties of the Heusler compound Co₂ScP have been investigated by the generalized gradient approximation based on density functional theory. The results show that the ground state phase of the Co₂ScP compound possesses AlCu₂Mn-type crystal structure and exhibits half-metallic ferrimagnetism. The total spin moment is 2 μ_B at the equilibrium lattice constant a₀=5.83 Å, which agrees with the Slater–Pauling rule. The spin-up electrons are metallic, but the spin-down bands are semiconductor with a gap of 0.55 eV, and the spin-flip gap is of 0.07 eV.     

First-principles study on the half-metallicity of zinc-blende CrP(1 1 0) surface

We have investigated the half-metallicity and magnetism at the (1 1 0) surface of CrP by using the all-electron full-potential linearized augmented plane wave (FLAPW) method within the generalized gradient approximation (GGA). From the calculated local density of states (LDOS), we found that the (1 1 0) surface of CrP preserves the half-metallicity, but the band gaps (∼1.1 eV) of the minority states for the surface Cr and P atoms are much reduced from the bulk value (∼1.9 eV). The magnetic moment of the P is coupled antiferromagnetically to that of the Cr. The magnetic moment of surface Cr atom is calculated to be 3.31μ_B which is increased by 10% compared to the bulk value, 3.00μ_B.     

Density functional study of oxygen adsorption on the Mg3Nd (0 0 1) surface

The adsorption of oxygen atoms on Mg₃Nd (0 0 1) surface was studied based on density function theory (DFT), in which the exchange-correlation potential was chosen as the generalized gradient approximation (GGA) in the Perdew and Wang (PW91). The most preferred adsorption position was at the top-hollow site. Upon the optimization on top-hollow site with different coverage, it was found that the adsorption energy decreased with oxygen coverage. The density of states analysis showed that obvious charge transfer took place between O atom and the nearest Nd atom and chemical bond formed between O atom and the nearest Nd atom after O adsorption. The result of surface energy as a function of chemical potential change of oxygen indicated the clean Mg₃Nd (0 0 1) surface was easy to adsorb oxygen and form 1.00 ML surface.     

Ruthenium adsorption and diffusion on the GaN(0 0 0 1) surface

We report first principles calculations to analyze the ruthenium adsorption and diffusion on GaN(0 0 0 1) surface in a 2×2geometry. The calculations were performed using the generalized gradient approximation (GGA) with ultrasoft pseudopotential within the density functional theory (DFT). The surface is modeled using the repeated slabs approach. To study the most favorable ruthenium adsorption model we considered T₁, T₄ and H₃ special sites. We find that the most energetically favorable structure corresponds to the Ru- T₄ model or the ruthenium adatom located at the T₄ site, while the ruthenium adsorption on top of a gallium atom (T₁ position) is totally unfavorable. The ruthenium diffusion on surface shows an energy barrier of 0.612 eV. The resultant reconstruction of the ruthenium adsorption on GaN(0 0 0 1)- 2×2 surface presents a lateral relaxation of some hundredth of Å in the most stable site. The comparison of the density of states and band structure of the GaN(0 0 0 1) surface without ruthenium adatom and with ruthenium adatom is analyzed in detail.     

First-principles study of structural, electronic and magnetic properties in Cd1−xFexS diluted magnetic semiconductors

In this paper, we report theoretical investigations of structural, electronic and magnetic properties of ordered dilute ferromagnetic semiconductors Cd_1−xFe_xS with x=0.25, 0.5 and 0.75 in zinc blende (B3) phase using all-electron full-potential linear muffin tin orbital (FP-LMTO) calculations within the density functional theory and the generalized gradient approximation. The analysis of band structures, density of states, total energy, exchange interactions and magnetic moments reveals that both the alloys may exhibit a half-metallic ferromagnetism character. The value of calculated magnetic moment per Fe impurity atom is found to be 4 μ_B. Moreover, we found that p-d hybridization reduces the local magnetic moment of Fe from its free space charge value of 4 μ_B and produces small local magnetic moments on Cd and S sites.     

First principles study of structural, electronic and vibrational properties of heavily boron-doped diamond

The structural, electronic and vibrational properties of a series of heavily B-doped diamond models have been investigated using the density functional theory within a local density approximation. The doped models C_64 − nB_n (n=1-3) were constructed using supercell techniques. The structural and electronic calculations confirmed that the B dimers are always energetically stable and electrical inactive. The superconducting transition temperature TC is not only decided by the B concentration, but also by the lattice configurations of boron atoms. The vibrational frequencies and eigenmodes were determined using the linear response approach, while Raman intensities were obtained by the second response method. The Raman analysis in terms of atomic vibrations found that the “500 cm⁻¹” and “1230 cm⁻¹” bands are both superposed bands including not only C vibrations but also B-B vibrations and B-C vibrations, respectively. The calculated Raman spectra with isotopic substitutions are in excellent agreement with corresponding experimental results. The reasonable explanation was provided for no obvious Raman shift of main bands from ¹⁰B¹²C to ¹¹B¹²C model.     

Electronic properties and compton profiles of silver iodide

We have carried out an extensive study of electronic properties of silver iodide in β- and γ-phases. The theoretical Compton profiles, energy bands, density of states and anisotropies in momentum densities are computed using density functional theories. We have also employed full-potential linearized augmented plane-wave method to derive the energy bands and the density of states. To compare our theoretical data, isotropic Compton profile measurement on γ-AgI using ¹³⁷Cs Compton spectrometer at an intermediate resolution of 0.38 a.u. has been undertaken. The theoretical anisotropies are also interpreted on the basis of energy bands.     

Spectroscopy of NdO: New results

¹⁴²NdO molecules have been produced by heating ¹⁴²Nd₂O₃ to about 2100 K in a vacuum furnace in the presence of argon gas. A ring dye laser operating with DCM dye has been used to excite ¹⁴²NdO transitions in the 636-666 nm spectral region, and induced fluorescence has been spectroscopically analysed at high resolution with a Fourier transform spectrometer. Contributions from thermal emission have been simultaneously observed. Two new low-lying electronic states have been detected, at energies of about 2708 and 4139 cm⁻¹, designated as [2.7], most probably observed at ν = 1, and [4.1], likely to be (2)6 (observed at ν = 0). The ν = 1 level of the (1)6 state, already known at ν = 0, has been observed for the first time. Most levels pumped by the laser, between 14 000 and 17 400 cm⁻¹, could be identified from earlier work. In addition, by studying in more detail recently obtained fluorescence spectra [J. Mol. Spectrosc. 225 (2004) 132] spectroscopic constants have been improved for a number of states. Finally, from thermal emission spectra, rotational analyses of the 0-0 bands of two new systems, [16.4] − (2)5 and [14.1] − X4, and reanalyses at higher resolution of the 0-0 bands of the systems V, VII, VIII, and X have been carried out. A consistent set of spectroscopic constants of the levels of ¹⁴²NdO characterized as yet is presented.     

Magnetic and electronic properties of NiAs-type chromium chalcogenides

We have computed spin-dependent energy bands, spin moments and density of states of NiAs-type CrX (X=S, Se and Te) chalcogenides using linear combination of atomic orbitals method within density functional theory as well as full potential augmented plane wave method. In addition, magnetic properties have also been computed using spin polarized relativistic Korringa-Kohn-Rostoker method. We have also obtained the first ever theoretical electron momentum densities of CrX compounds considering linear combination of atomic orbitals and compared the results with the isotropic Compton profiles measured using 20 Ci ¹³⁷Cs Compton spectrometer. The Fermi surface topology and magnetic properties are discussed in terms of majority and minority energy bands and density of states. In addition, to highlight the role of Cr (3d) electrons in such type of chalcogenides, we have also reported the magnetic Compton profile of CrTe using the Korringa-Kohn-Rostoker method.     

Anisotropy in the Compton profiles of Nb and NbH0.76

The Compton profiles of Nb and NbH_0.76 single crystals have been measured along [100] and [110] using 412 keV gamma-radiation from a¹⁹⁸Au source. The changes in the band electron profile of the metal following the introduction of hydrogen are interpreted in terms of the protonic model of the hydride. Qualitative changes in the directional profiles can be understood within the rigid band approximation.     

Effect of deposition pressure on structural, optical and electrical properties of zinc selenide thin films

ZnSe thin films have been prepared by inert gas condensation method at different gas pressures. The influence of deposition pressure, on structural, optical and electrical properties of polycrystalline ZnSe films have been investigated using X-ray diffraction (XRD), optical transmission and conductivity measurements. The X-ray diffraction study reveals the sphalerite cubic structure of the ZnSe films oriented along the (1 1 1) direction. The structural parameters such as particle size [6.65-22.24 nm], strain [4.01-46.6×10⁻³ lin⁻² m⁻⁴] and dislocation density [4.762-18.57×10¹⁵ lin m⁻²] have been evaluated. Optical transmittance measurements indicate the existence of direct allowed optical transition with a corresponding energy gap in the range 2.60-3.00 eV. The dark conductivity (σ_d) and photoconductivity (σ_ph) measurements, in the temperature range 253-358 K, indicate that the conduction in these materials is through an activated process having two activation energies. σ_d and σ_ph values decrease with the decrease in the crystallite size. The values of carrier life time have been calculated and are found to decrease with the reduction in the particle size. The conduction mechanism in present samples has been explained, and the density of surface states [9.84-21.4×10¹³ cm⁻²] and impurity concentration [4.66-31.80×10¹⁹ cm⁻³] have also been calculated.     

First-principles study on the electronic and optical properties of SnxGe1 − x

The electronic and optical properties of the direct band gap alloys Sn_xGe_1 − x (x = 0.000, 0.042, 0.083, 0.125, 0.167, and 0.208) have been studied by using the generalized gradient approximation in the framework of the density functional theory. The calculated lattice constants obey Vergard's law. The band structures show that the alloys have direct band gap and the band gaps can be tunable by Sn contents. The optical properties of the Sn_xGe_1 − x alloys with the physical quantities such as the complex dielectric function, the energy-loss function and the static dielectric constant, respectively, are shown to support the potential application of infrared devices in the future.