Effect of impurity atoms on α2/γ lamellar interfacial misfit in Ti–Al alloy: a systematic first principles study

The effect of transition metal solutes on the lattice parameters of γ-TiAl and α₂-Ti₃Al were studied by first principles calculations to find suitable elements for controlling the α₂/γ interfacial misfit in lamellar Ti–Al alloys. Better agreement was found between the calculated and experimental phase and site preferences of impurity atoms than in a previous first principles study. The calculated lattice parameters suggest that elements in groups 6–11 of the 4th period (Cr, Mn, Fe, Co, Ni and Cu) are effective for increasing the misfit, leading to increasing density of misfit dislocation and, in turn, higher yield strength and ductility. This effect is caused by the change in the lattice parameter of the γ-TiAl phase rather than those of α₂-Ti₃Al phase. This prediction agrees qualitatively with experimental data from a previous study although the effects of temperature are not taken into account. Further improvements should be possible by considering those effects. Nevertheless, the results highlight the effects of impurity addition on interfacial misfit at a level which cannot be achieved by classical concepts such as atomic size in a hard sphere model. The results will also be valuable in further more quantitative predictions and in understanding the effects of temperature, including off-stoichiometry, thermal expansion and vibration entropy.     

Effects of ⅢB transition metals on optoelectronic and magnetic properties of HoMnO_3: A first principles study

The optoelectronic and magnetic properties of pure Ho Mn O3 and Ho0.67T0.33 Mn O3(T = La, Y) alloys in hexagonal phase are theoretically investigated by using the first-principles calculations. The investigations are performed by means of the density functional theory through using the spin polarized generalized gradient approximation plus the Hubbard potential(SPGGA + U, U eff= 3 eV). The studied material Ho MnO3 exhibits two indirect band gaps: 1.58 eV for the spinup state and 0.72 eV for the spin-down state along the S–G direction within the SPGGA + U approximation. It is found that the band gap of pure Ho Mn O3 for the spin-up state increases with increasing La and Y dopants. The results show that all of the studied materials have semi-metallic behaviors for the spin-up state and semiconducting character for the spin-down state. The substitutions of La and Y for Ho in Ho MnO3 cause the static dielectric constant(ε0) to increase in the x direction but to decrease in the z direction. The calculated optical conductivity spectrum of Ho MnO3 in a low energy range is in good agreement with the recent experimental data.     

Interactions between vacancies and prismatic Σ3 grain boundary in α-Al_2O_3:First principles study

Interactions between vacancies and Σ3 prismatic screw-rotation grain boundary in α-Al_2O_3 are investigated by the first principles projector-augmented wave method.It turns out that the vacancy formation energy decreases with reducing the distance between vacancy and grain boundary(GB) plane and reaches the minimum on the GB plane(at the atomic layer next to the GB) for an O(Al) vacancy.The O vacancy located on the GB plane can attract other vacancies nearby to form an O–O di-vacancy while the Al vacancy cannot.Moreover,the O–O di-vacancy can further attract other O vacancies to form a zigzag O vacancy chain on the GB plane,which may have an influence on the diffusion behavior of small atoms such as H and He along the GB plane of α-Al_2O_3.     

Phase stability,electronic, magnetic and elastic properties of Ni2CoZ(Z = Ga,Sn): A first principles study with GGA method and GGA+U approach

First principles calculations based on density functional theory are used to investigate the phase stability, electronic, magnetic and elastic properties of ferromagnetic metallic full-Heusler Ni₂CoZ(Z = Ga, Sn) alloys via the FP-LAPW method by the generalized gradient GGA and GGA+U approximations for the exchange and correlation energy, within the Perdew–Burke–Ernzerhof (PBE 96) parameterization. The results of calculating electronic structures and magnetic properties reveal that the both Ni₂CoGa and Ni₂CoSn crystallize in L2₁ phase with regular cubic structure. The two investigated compounds exhibit metallic ferromagnetic behaviors for the GGA+U calculation. The computation of elastic constants with GGA+U approach shows that our compounds are mechanically stable.     

Structural evolutions and electronic properties of Au_nGd(n=6–15) small clusters: A first principles study

Structural, electronic, and magnetic properties of Au_nGd(n = 6–15) small clusters are investigated by using first principles spin polarized calculations and combining with the ab-initio evolutionary structure simulations. The calculated binding energies indicate that after doping a Gd atom Aun Gd cluster is obviously more stable than a pure Au_(n+1) cluster.Au_6Gd with the quasiplanar structure has a largest magnetic moment of 7.421 μ_B. The Gd-4 f electrons play an important role in determining the high magnetic moments of Au_nGd clusters, but in Au_6Gd and Au_(12) Gd clusters the unignorable spin polarized effects from the Au-6 s and Au-5 d electrons further enhance their magnetism. The HOMO–LUMO(here, HOMO and LUMO stand for the highest occupied molecular orbital, and the lowest unoccupied molecular orbital, respectively)energy gaps of Au_nGd clusters are smaller than those of pure Au_(n+1) clusters, indicating that Au_nGd clusters have potential as new catalysts with enhanced reactivity.     

Simulation of structured 4T1→6A1 emission bands of Mn2+ impurity in Zn2SiO4: A first-principle methodology

A sequential, fully first-principle theoretical study of the Mn²⁺ green emission bands in the Zn₂SiO₄:Mn²⁺ phosphor is presented for the first time. A combined approach is developed based on the modern periodic density-functional theory and cluster ab initio wave-function-based electronic structure methods, the linear response theory for lattice phonons, and generating function formalism of vibronic spectra within the displaced multi-mode harmonic oscillator model. We obtain fairly good agreement between the calculated low- and high-temperature emission band positions, widths, zero-phonon lines and phonon wings and the available experimental emission studies, with special emphasis on Mn²⁺ distribution over two non-equivalent Zn²⁺ sites in the Zn₂SiO₄ material. An interpretation for vibronic structure observed in the low-temperature emission spectrum of this phosphor is suggested based on the present first-principle study.     

Experimental and ab initio study of the nuclear quadrupole interaction of 181 Ta-probes in an α-Fe2O3 single crystal

We report perturbed-angular-correlation (PAC) experiments on ¹⁸¹Hf (→¹⁸¹Ta)-implanted corundum α-Fe₂O₃ single crystal in order to determine the magnitude, symmetry and orientation of the electric-field-gradient (EFG) tensor at Ta donor impurity sites of this semiconductor. These results are analyzed in the framework of ab initio full-potential augmented-plane wave plus local orbital (FP-APW+lo) calculations. This combined analysis enables us to quantify the magnitude of the lattice relaxations induced by the presence of the impurity and to determine the charge state of the impurity donor level introduced by Ta in the band gap of the semiconductor.     

Structural properties and 4f → 5d absorptions in Ce-doped LuAlO?: a first-principles study

The structural properties and the 4f → 5d absorptions of Ce-doped LuAlO(3) have been studied using the density functional theory-based generalized gradient approximation PBE + U (PBE: Perdew, Burke and Ernzerhof) and wavefunction-based embedded cluster calculations, respectively. The PBE or PBE + U calculations reveal that the substitution of Ce for Lu induces a strongly anisotropic distortion of the local atomic structure around the dopant site, which is largely insensitive to the value of U for the Ce 4f states. The calculated electronic structures depend explicitly on the value of U, and a value of U ≈ 6 eV is determined by comparison with experimental x-ray photoelectron data for CeAlO(3). On the basis of the PBE-optimized structure, CASSCF/CASPT2 (complete-active-space self-consistent-field/second-order perturbation theory) embedded cluster calculations for the Ce(3+) 4f → 5d transitions yield energy and intensity patterns in fairly good agreement with those estimated from the experimental absorption spectrum. A Mulliken spin population analysis for the 5d(1) states shows that the origins of the states are significantly different from being caused by the cubic crystal field, confirming an earlier conclusion as regards the origin of the 5d(1) states based on semiempirical molecular orbital calculations. The importance of spin-orbit effects on the energies and wavefunctions of the Ce 5d(1) states is highlighted.     

A first principles study of the adsorption and dissociation of CO<Subscript>2</Subscript> on the δ-Pu (111) surface

A complete understanding of the nature of the 5f electrons has been and continues to be a major scientific problem in condensed matter physics. Bulk and surface electronic structure studies of the actinides as also atomic and molecular adsorptions on the actinide surfaces provide a path towards this understanding. In this work, ab initio calculations within the framework of density functional theory have been used to study the adsorption of molecular CO₂ and the corresponding partially dissociated (CO + O) and completely dissociated (C + O + O) products on the δ-Pu (111) surface. The completely dissociated C + O + O configurations exhibit the strongest binding with the surface (7.92 eV), followed by partially dissociated products CO + O (5.08 eV), with molecular CO₂ adsorption having the lowest binding energies (2.35 eV). For all initial vertically upright orientations, the CO₂ molecule physisorbs or do not bind to the surface and the geometry and orientation do not change. For all initial flat lying orientations chemisorption occurs, with the final state corresponding to a bent CO₂ molecule with bond angles of 117°–130° and the elongation of the CO bond. For CO + O co-adsorption, the stable configurations corresponded to CO dipole moment orientations of 100°–172° with respect to the surface normal and the elongation of the CO bond. The most stable chemisorption cases correspond to anomalously large rumpling of the top Pu layer. The interactions of the CO₂ and CO with the Pu surface have been analyzed using the energy density of states and difference charge density distributions. The nature and the behavior of the 5f electrons have also been discussed in detail in the context of this study.     

The behaviour of superparamagnetic small particles in applied magnetic fields: A Mössbauer spectroscopic study of ferritin and haemosiderin

Small magnetically ordered particles display characteristic temperature dependent superparamagnetic behaviour in their Mössbauer spectra, as a result of the interplay between the thermal energy and the magnetic anisotropy energy of each particle. In the presence of an applied magnetic field there is an additional energy term arising from the net magnetic moment of the particles. The resulting Mössbauer spectra depend on the size of the anisotropy energy relative to the energy of the magnetic moment of the particles in the applied field. The present applied field Mössbauer measurements on ferritin and haemosiderin indicate that in these materials the anisotropy energy dominates, although the spectra can still be analysed to give information on the magnetic moment of the particles.     

A computational study of N2···HHeF: comparison with N2···HArF and N2···HKrF

A weakly bound linear complex of N₂ and HHeF was found to be stable with respect to the constituent monomers by ab initio calculations at various levels of theory (MP2, MP3, MP4(SDQ) and QCISD) using a 6-311++G(2d,2p) basis set. The complex N₂···HHeF was found to have a zero-point vibrational energy corrected binding energy of 14.5?kJ mol^?1 (QCISD) and exhibits a large harmonic vibrational frequency blue shift of 375?cm^?1 for the He–H stretching vibration mode, with a diminished infrared intensity for this mode on formation of the complex. The frequency shift for this mode was also found to be very sensitive to the level of theory employed for the calculation, and is rationalized by considering intermolecular electrostatic and charge-transfer effects. The results for N₂···HHeF are compared with corresponding results for the related complexes N₂···HArF and N₂···HKrF, both of which contain the same proton acceptor molecule.     

Co-adsorption of O_2 and H_2O on α-uranium(110) surface:A density functional theory study

First-principles calculations based on density functional theory corrected by Hubbard parameter U(DFT+U) are applied to the study on the co-adsorption of O2 and H_2O molecules to α-U(110) surface. The calculation results show that DFT+U method with Ueff= 1.5 e V can yield the experimental results of lattice constant and elastic modulus of α-uranium bulk well. Of all 7 low index surfaces of α-uranium, the(001) surface is the most stable with lowest surface energy while the(110) surface possesses the strongest activity with the highest surface energy. The adsorptions of O_2 and H_2O molecules are investigated separated. The O_2 dissociates spontaneously in all initial configurations. For the adsorption of H_2O molecule,both molecular and dissociative adsorptionsoccur. Through calculations of co-adsorption, it can be confirmed that the inhibition effect of O_2 on the corrosion of uranium by water vapor originates from the preferential adsorption mechanism,while the consumption of H atoms by O atoms exerted little influence on the corrosion of uranium.     

Diffusion of a Ga adatom on the GaAs(001)‐c(4 × 4)‐heterodimer surface: A first principles study

The adsorption and diffusion behavior of a Ga adatom on the GaAs (001)‐c(4 × 4)-heterodimer surface were studied by employing ab initio density functional theory (DFT) computations in the local density approximation. Structural and bonding features of the c(4 × 4)-heterodimer reconstruction surface were examined. A comparison with the c(4 × 4)-ss reconstruction was performed. Minimum energy sites (MES) on the c(4 × 4)-heterodimer surface were located by mapping the potential energy surface for a Ga adatom. Barriers for diffusion of a Ga adatom between the neighboring MES were calculated by using top hopping- and exchange-diffusion mechanisms. We proposed two unique diffusion pathways for a Ga adatom diffusing between the global minimums of two neighboring unit cells. Signature differences between electronic structures of top hopping- and exchange‐diffusion mechanisms were studied for relevant atoms. We observed a higher diffusion barrier for exchange mechanism compared to top hopping.     

Hyperfine structures and isotope shifts of the 5d 4 D 7/2→6p 4 P 5/2 0 transition in Xenon ions

Collinear fast beam-laser spectroscopy has been performed on metastable 5d ⁴ D _7/2 Xenon ions. Hyperfine structure constants for the 6p ⁴ P _5/2 ⁰ level have been derived for¹²⁹Xe:A=?1,634.9±0.9 MHz and¹³¹Xe:A=485.3±0.3 MHz andB=?116.5±2.0MHz. Changes in mean squared nuclear charge radii are derived from the measured isotope shifts.     

Influences of Li Intercalation on the Electronic Structures of O2p and V3d Orbitals in α-V2O5

运用第一性原理计算了锂嵌入对α-V₂O₅中O2p和V3d轨道电子结构的影响. 计算结果表明,不同的锂嵌入位置对O2p和V3d轨道的电子结构有着不同的影响. 但锂的嵌入会减弱了V₂O₅中V=O1键,同时导致V3d导带的劈裂变窄或消失和O2p价带变宽. 最后计算出从每个Li2s轨道到V3d轨道的电子传递数为0.52.     

Study of phase transition in a [CdHgI4 : 0.2AgI] mixed conducting composite system doped with KI and K2SO4

New composite superionic systems, [CdHgI₄?:?0.2AgI]?:?0.xKI and [CdHgI₄?:?0.2AgI]?:?0.xK₂SO₄ (x?=?0.2, 0.4, 0.6?mol. wt%), were prepared, using [CdHgI₄?:?0.2AgI] mixed composite system as the host. Electrical conductivity was measured to study the transition behavior at frequencies of 100?Hz, 120?Hz, 1?kHz, and 10?kHz in the temperature range from 150°C to 250°C using a GENRAD 1659 RLC Digibridge. A sharp increase in conductivity was observed during β?→?α phase transition. Upon increasing the dopant-to-host ratio, the conductivity of the superionic systems exhibited Arrhenius (thermally activated)-type behavior. Differential thermal analysis, differential scanning calorimetry, thermogravimetric analysis, and X-ray powder diffraction were performed to confirm the doping effect and transition in the host. The phase transition temperature increased with an increase in the dopant concentration. Activation energies in eV for pre- and post-transition phase behavior are reported.