New insights into the anti-disproportionation mechanism of ZrCo alloying with Ti,Hf, Sc,Cu, and Fe elements

First-principles calculations were performed to investigate the effects of alloying substitutions (i.e. Ti, Hf, Sc, Cu and Fe) on the anti-disproportionation ability of ZrCo alloy. For the first time, we revealed the disproportionation mechanism from the energy point of view and provided a new theoretical method to predict whether the substitution element has the ability to enhance the anti-disproportionation performance of ZrCo alloy. Based on the hydrogen atom occupancy behavior in ZrCoH₃ and the results of our calculation of binding energy, the hydrogen atom migration model during hydrogenation and theoretical computational model were established. Through structural optimization, a series of stable 2 × 1 × 2 ZrCoH₃ supercells were obtained, which contain four hydrogen atoms occupying 8e site and various substitution atoms with different amounts except for pure system. The binding energy of hydrogen atom in the 8e site and activation energy of diffusing from 8e site to 4c₂ site of these ZrCoH₃ supercells were calculated. The results showed that the substitution of Ti and Hf increased the binding energy of hydrogen atom in the 8e site, while the substitution of Fe, Cu and Sc decreased the binding energy of hydrogen atom in the 8e site. Meanwhile, both of Ti and Hf substitution reduced the activation energy of diffusing from 8e site to 4c₂ site, while all of Fe, Cu and Sc substitution increased the activation energy of diffusing from 8e site to 4c₂ site. These results indicated that hydrogen-induced disproportionation was the inherent property of ZrCo alloy, and element substitution can restrain or accelerate disproportionation by affecting both the binding energy and activation energy. With simultaneous consideration of the binding energy and activation energy, the effect of these alloying substitutions on the anti-disproportionation ability could be ascertained and the results were in good agreement with the previous theoretical and experimental results.     

Hydrogen diffusion and anti-disproportionation properties in ZrCo alloys: The effect of Sc,V, and Ni dopants

The use of ZrCo alloys as hydrogen isotope storage materials is limited by the significant reduction of storage capacity caused by disproportionation reaction. In this study, the effects of Sc/V/Ni substitution on the hydrogen diffusion and anti-disproportionation properties of ZrCo alloys and their hydrides were systematically investigated by theoretical calculations. The doping of V reduces the migration barrier of absorbed H at different octahedral sites, leading to improved hydrogen permeability and fast kinetics. For ZrCoH₃ hydrides, V/Ni dopant increases the formation energy of H in 8e site, while Sc has opposite effect. Additionally, the migration barrier for H away from 8e site to its nearby 4c₂ site is obviously lowered by V, but is increased by Sc/Ni. These results indicate that V substitution can effectively improve hydride anti-disproportionation capability, which deepens the understanding of experimental phenomena, and sheds valuable light on the design of ZrCo alloys with high performance.     

Effects of Mo substitution on the kinetic and thermodynamic characteristics of ZrCo1-xMox (x = 0–0.2) alloys for hydrogen storage

In this study, ZrCo_1-xMo_x (x = 0, 0.05, 0.1, 0.15, 0.2) alloys were prepared via vacuum arc-melting method. The effects of substituting Co with Mo on the structure, initial activation behaviors, and thermodynamic properties of the afore-mentioned alloys were systematically investigated. The results showed that ZrCo_1-xMo_x (x = 0, 0.05, 0.1, 0.15) alloys exhibited a single ZrCo phase and their corresponding hydrides, a ZrCoH₃ phase. Furthermore, ZrCo_0.8Mo_0.2 alloy consisted of ZrCo phase and a trace of ZrMo₂ phase, and the hydride contained ZrCoH₃ and ZrH phases. As the Mo content was increased, the initial activation period decreased significantly from 19277 s for ZrCo to 576 s for ZrCo_0.8Mo_0.2, which was closely related to the catalytic effect of ZrMo₂. The plateau width of pressure composition temperature curves were shortened, and the equilibrium pressures of hydrogen desorption decreased slightly as Mo content increased. Additionally, the experiments showed that the anti-disproportionation performance was greatly improved by Mo substitution. The extent of disproportionation decreased from 64.28% for ZrCo to 24.11% for ZrCo_0.8Mo_0.2. The positive effect of Mo substitution on improving the anti-disproportionation property of ZrCo alloy was attributed to the reduction of hydrogen atom in 8f₂ and 8e sites, which decreased the driving force of the disproportionation reaction.     

A new strategy for remarkably improving anti-disproportionation performance and cycling stabilities of ZrCo-based hydrogen isotope storage alloys by Cu substitution and controlling cutoff desorption pressure

ZrCo_1-xCu_x (x = 0–0.3) alloys for hydrogen isotope storage were prepared via induction levitation melting. The effects of partial substitution of Cu for Co on the microstructure, hydrogen storage properties including hydriding-dehydriding kinetics, thermodynamic characteristics, cycling stability and related mechanism have been systematically investigated. It is found that all synthesized alloy ingots consist of ZrCo main phase, the grain size is further refined but the segregation of Cu element at grain boundary is more serious with the increase of Cu content. The pressure-composition isotherms for dehydrogenation show that both ZrCoH₃ and ZrCo_0.9Cu_0.1H₃ hydrides undergo one-step desorption, while ZrCo_0.8Cu_0.2H₃ and ZrCo_0.7Cu_0.3H₃ hydrides experience two-step desorption since a new middle hydride phase of ZrCoH_0.8 with CrB-type orthorhombic structure is discovered during their dehydrogenation. This result is proposed to be linked with the changed electronic structure and lattice distortion induced by Cu substitution. To compare their dehydriding kinetics, the apparent activation energies for hydrogen desorption of different hydride phases in the alloys are also calculated systematically, and the value of E_a for hydrogen desorption of ZrCoH₃ phase is decreased from 118.02 kJ/mol to 95.90 kJ/mol, 77.98 kJ/mol and 78.65 kJ/mol, respectively. Prominent cycling stabilities of the Cu-substituted alloys are obtained and follow the trend: ZrCo_0.8Cu_0.2 > ZrCo_0.7Cu_0.3 > ZrCo_0.9Cu_0.1 > ZrCo. Specifically, the optimum cycling stable capacity of ZrCo-based alloy is increased from 0.4 wt % to 1.21 wt %. Furthermore, the ZrCo_0.8Cu_0.2 alloy exhibits further enhanced cycling stability during the cycle by controlling cutoff desorption pressure at 0.253 bar, where only the first-step dehydrogenation happens. Therefore, a new strategy for improving anti-disproportionation performance of ZrCo-based alloys by controlling cutoff desorption pressure is also proposed, which is in favor of the enhanced cycling stability and further application of Cu-substituted ZrCo-based alloys for hydrogen isotope storage and delivery in the International Thermonuclear Experimental Reactor (ITER).     

First-principles investigation on the role of interstitial site preference on the hydrogen-induced disproportionation of ZrCo and its doped alloys

There are two phase structures involved in ZrCo hydrides (ZrCoH_x). When x ≤ 1, the α-phase hydride is generated when hydrogen atoms occupy the 3c and 12i sites. When 1 < x ≤ 3, three interstitial sites of 4c₂, 8f₁, and 8e are occupied by H, and in turn the β-phase hydride is formed. There is a disproportionation reaction in β-phase hydrides during hydrogen discharging process to produce the ZrH₂ phase with higher thermal stability, leading to inferior hydrogen storage performance. In this study, the influence of hydrogen storage capacity on thermodynamic and lattice stabilities of α- and β-phase hydrides for each occupancy position is investigated under the framework of the first-principles study. The results indicate that the binding energy in the 3c site is higher compared with the 12i site under the condition of identical hydrogen storage capacity. Similarly, the binding energy is the largest for the 8e site compared with the other two sites, indicating that there is the least energy released in the reaction process. Thus, the 8e site is proved as the most unfavorable site in β-phase ZrCo hydrides, which is due to its degraded thermodynamic stability. Also, comparisons of mechanical properties and total density of states for each site in two hydride phases are presented to demonstrate that compound lattice stability in the 8e site is the poorest, suggesting that it is more likely to produce disproportionation. Furthermore, the dependence of hydrogen storage performance of β-phase hydrides on Ti/Rh doping is examined as well. It is discovered that there is improved thermodynamic stability and lattice stability in the 8e site for Zr_0.875Ti_0.125Co after Zr is partially substituted by Ti, which significantly enhances the disproportionation resistance. In contrast, when Co is partially replaced by Rh, there is a deterioration in the thermodynamic stability of ZrCo_0.875Rh_0.125 in the 8e site, but its lattice stability is somewhat improved.     

Engineering the hydrogen storage properties of the perovskite hydride ZrNiH3 by uniaxial/biaxial strain

In the present work, the bonding length, electronic structure, stability, and dehydrogenation properties of the Perovskite-type ZrNiH₃ hydride, under different uniaxial/biaxial strains are investigated through ab-initio calculations based on the plane-wave pseudo-potential (PW-PP) approach. The findings reveal that the uniaxial/biaxial compressive and tensile strains are responsible for the structural deformation of the ZrNiH₃ crystal structure, and its lattice deformation becomes more significant with decreasing or increasing the strain magnitude. Due to the strain energy contribution, the uniaxial/biaxial strain not only lowers the stability of ZrNiH₃ but also decreases considerably the dehydrogenation enthalpy and decomposition temperature. Precisely, the formation enthalpy and decomposition temperature are reduced from ?67.73 kJ/mol.H₂ and 521 K for non-strained ZrNiH₃ up to ?33.73 kJ/mol.H₂ and 259.5 K under maximal biaxial compression strain of ε = ?6%, and to ?50.99 kJ/mol.H₂ and 392.23 K for the maximal biaxial tensile strain of ε = +6%. The same phenomenon has been also observed for the uniaxial strain, where the formation enthalpy and decomposition temperature are both decreased to ?39.36 kJ/mol.H₂ and 302.78 K for a maximal uniaxial compressive strain of ε = - 12%, and to ?51.86 kJ/mol.H₂ and 399 K under the maximal uniaxial tensile strain of ε = +12%. Moreover, the densities of states analysis suggests that the strain-induced variation in the dehydrogenation and structural properties of ZrNiH₃ are strongly related to the Fermi level value of total densities of states. These ab-initio calculations demonstrate insightful novel approach into the development of Zr-based intermetallic hydrides for hydrogen storage practical applications.     

Temperature-hydrogen pressure phase boundaries and corresponding thermodynamics for ZrCoH system

The thermodynamically and kinetically stable regions of the temperature–H₂ pressure phase boundaries for the ZrCoH system were established using the Temperature-Concentration-Isobar (TCI) method. Based on this, the enthalpy change and entropy change values of dehydrogenation and disproportionation reactions were successfully obtained. The average enthalpy change (ΔH) and entropy change (ΔS) estimated from the phase boundaries for dehydrogenation of ZrCoH₃ to ZrCo are respectively 103.07 kJ mol^?1H₂ and 148.85 J mol^?1 H₂ K^?1, which are well agreement with the data reported in literature. The average ΔH and ΔS were estimated to be ?120.91 kJ mol^?1H₂ and -149.32 J mol^?1 H₂ K^?1 for the disproportionation of ZrCoH₃, whereas the ΔH and ΔS were calculated to be ?84.6 kJ mol^?1H₂ and -92.29 J mol^?1 H₂ K^?1 for disproportionation of ZrCo. In addition, it was found from the established phase boundaries that the anti-disproportionation property of ZrCo alloy can be enhanced if the phase boundaries of hydrogenation/dehydrogenation are far away from the phase boundaries of disproportionation by adjusting the thermodynamics. Meanwhile, it is possible to keep ZrCo away from disproportionation even at high temperature of 650 °C under hydrogen atmosphere, if the temperature-H₂ pressure trajectory is carefully controlled without crossing the phase boundaries of disproportionation. Therefore, the established phase boundaries can be used as a guide to the eye avoiding disproportionation and improving the anti-disproportionation property of ZrCo alloy.     

The electronic properties and structural stability of LaFeO3 oxide by niobium doping: A density functional theory study

The niobium doping perovskite has been used in anode materials of solid oxide fuel cell. The electronic properties and structural stability of LaFeO₃ (LFO) oxide by Nb-doping and the adsorption of H₂ molecule at the clean and Nb-doped LFO (001) surface are investigated by theoretical calculations. The calculated results reveal that the band gap of the orthorhombic LFO is 2.04 eV and the gap disappears after the Nb-doping, which improves the electrical conductivity. The Nb-doping increases the formation energy of oxygen vacancy in orthorhombic LFO. The calculated results of binding energy and formation enthalpy imply that the structural stability is strengthened after Nb-doping, which provides a theoretical explanation for recent experimental observations. This result can be attributed to the change of electronic structure after the Nb-doping. The bond mechanisms for LFO and Nb-doped LFO are obtained by analyzing density of states, Mulliken charges and bond population. Based on adsorption properties, it can be found that the adsorption of H₂ molecule is slightly enhanced after Nb-doping and the Nb-doping facilitates that H₂ molecule dissociates to H atoms. These results could provide powerful interpretations for the origin of experimental phenomenon.     

An integrated computational and experimental method for predicting hydrogen plateau pressures of TiFe1-xMx-based room temperature hydrides

First-principles density functional theory (DFT) calculations were performed to investigate the effect of ternary alloying on the hydrogenation properties of the TiFe system. Al, Be, Co, Cr, Cu, Mn and Ni were selected as substitutional elements for Fe sites, in the light of their reported enhancement of activation, kinetic and thermodynamic properties. The use of special quasi-random structures to account for disordering of solute elements in the sub-lattice allowed a quantitative assessment of substitutional effects on the hydrogenation behaviour of single-phase TiFe_1-xM_x alloys, up to a solute concentration as high as 40 at.%. The energy of monohydride formation obtained by DFT calculations, approximated to the enthalpy of formation, was discussed in terms of changes in lattice parameter and hence plateau pressure. Based on the consistency between DFT calculations and earlier experimental results, a linear relationship between monohydride formation energy/enthalpy and plateau pressure was proposed as a simple method to predict the value of one of these physical properties from the other. The obtained correlation could therefore turn out to be a helpful tool to predict the ab/desorption plateau pressure of unexplored vast multi-component systems from DFT calculation, or, the other way around, could allow to estimate the formation enthalpy from only one pressure-composition-isotherm (PCI) measurement hence without the need of Van't Hoff plot.     

An ab initio study of spectroscopic and thermodynamic characteristics of MgH2 and TiC systems

In this investigation, structural, dynamical and thermodynamic characteristics of magnesium hydride (MgH₂) and titanium carbide (TiC) are performed through first principle calculations based on the density functional theory (DFT). The lattice dynamics were investigated using the finite displacement supercell approach and thermodynamic calculations were carried out using the harmonic approximation. The modes of vibrations were studied to explore the behavior of individual atoms. The minimum hydrogen release temperature was noted to be Tc = 719 K when only electronic and vibrational free energies of MgH₂ and TiC systems are considered at pressure of 1 bar. However, a remarkable reduction in hydrogen release temperature is noticed in MgH₂ and TiC system i.e. Tc = 321 K (fall of 398 K) by including all the contributions of free energies (i.e. electronic, translational, rotational and vibrational) of hydrogen molecule.     

Achieving high performance for aluminum stabilized Li7La3Zr2O12 solid electrolytes for all solid‐state Li‐ion batteries: A thermodynamic point of view

For the solid‐state reaction synthesis of Al containing Li₇La₃Zr₂O₁₂, various precursors have been used. Since there is a lack of general agreement for choosing precursors, a quantitative approach to build a consensus is required. In this study, a thermodynamic point of view for selecting the precursors in the field of Li₇La₃Zr₂O₁₂ synthesis was covered according to the Gibbs free energy and enthalpy change of precursors' decomposition reactions. In terms of Gibbs free energy change calculations, LiOH, La(OH)₃, and Al(OH)₃ were favorable whereas, LiOH, La₂O₃, and Al(OH)₃ were the preferred precursors for the enthalpy change calculations. Pellets prepared by using the favored precursors calculated from enthalpy change showed improved densification, higher ionic conductivity (2.11 × 10^?4 S/cm), and lower activation energy (0.23 eV) compared with Gibbs free energy change. As a thermodynamically favored aluminum precursor, Al(OH)₃ was discussed in the present study and hinders the ionic conductivity in comparison to Al₂O₃.     

Systematical study on the roles of transition alloying substitutions on anti-disproportionation reaction of ZrCo during charging and releasing hydrogen

Intermetallic alloy ZrCo is believed to be a good substitution for uranium to store tritium. Nevertheless, disproportionation reaction often happens during the hydriding and dehydriding processes, and hydrogen storage property of ZrCo is therefore degraded. Alloying elements are often used to substitute Zr or Co in ZrCo to restrain disproportionation reaction. However, many experimental results do not agree with each other, and it lacks overall tendency for all transition metal elements. In this work, systematical ab initio calculations are performed to study more than 20 transition alloying elements to substitute Co and Zr in ZrCoH₃ to study the anti-disproportionation effects. It is found that substitution of Co by transition metal elements on anti-disproportionation reaction is unconspicuous, and only Ni can enlarge Zr–H bond length and decrease the volume of 8e site, presenting anti-disproportionation effect, which qualitatively agrees with the previous experiments. In contrast, all transition alloying elements considered except Fe, Co, Ni, Ru, Rh, Pd, Os and Ir replacing Zr can both enlarge the length of Zr–H bond and decrease the volume of 8e site, and thus restrain the disproportionation effects. At last, two-dimensional charge density and density of states are calculated to analyze the underlying mico-mechanisms affecting the effects of transition alloying elements on anti-disproportionation reaction.     

Ab initio calculations on energetics and electronic structures of cubic Mg3MNi2 (M = Al, Ti, Mn) hydrogen storage alloys

Mg₃MNi₂ (M = Al, Ti, Mn) ternary intermetallic compounds with cubic structure are a new type of potential hydrogen storage alloys. Using ab initio density functional theory (DFT) calculations, the energetics and electronic structures of Mg₃MNi₂ (M = Al, Ti, Mn) compounds are systematically investigated. The optimized structural parameters including lattice constants and internal atomic positions are close to experimental data determined from X-ray powder diffraction. The calculated results of formation enthalpy ΔH_form show that the stabilities of cubic Mg₃MNi₂ (M = Al, Ti, Mn) compound, compared with hexagonal Mg₂Ni, increase in the order of Mg₃MnNi₂, Mg₂Ni, Mg₃TiNi₂ and Mg₃AlNi₂, whereas the stabilities of their saturated Mg₃MNi₂H₃ (M = Al, Ti, Mn) hydrides, compared with monoclinic Mg₂NiH₄, decrease in the order of Mg₂NiH₄, Mg₃AlNi₂H₃, Mg₃TiNi₂H₃ and Mg₃MnNi₂H₃. Further calculations of hydrogen desorption enthalpy ΔH_des indicate that these cubic Mg₃MNi₂ (M = Al, Ti, Mn) compounds possess promising dehydrogenation properties for their relatively lower ΔH_des values. Among of them, the dehydrogenation ability of Mg₃TiNi₂ is the most pronounced. Analysis of electronic structures suggests that the strong covalent bonding interactions between Ni and M within cubic Mg₃MNi₂ (M = Al, Ti, Mn) are dominant and directly control the structural stabilities of these compounds.     

Improved thermodynamic properties of doped LiBH4 for hydrogen storage: First-principal calculation

First-principles calculations have been performed on lithium borohydride LiBH₄ using the ultrasoft pseudopotential method, which is a potential candidate for hydrogen-storage materials due to its extremely large gravimetric capacity of 18 mass % hydrogen. We focus on an orthorhombic phase observed at ambient conditions and predict its fundamental properties; De-hydrogenation and electronic properties of doped Li_1+xB_1−xH₄ by Li (with 0 < x < 0.75); to be used as a material for hydrogen-storage; are studied from density-functional theory based first-principles calculations. The results suggest that the substitution of B by Li decrease the desorption enthalpy of hydrogen from 75 kJ/mol.l to 40. Our calculation results show the function of Li in improving thermodynamics, which provides a favorable thermodynamic modification.     

Remarkable enhancement in durability of ZrCo alloy against hydrogen induced disproportionation by Ti and Nb co-substitution

Considering the thermodynamic stability of various hydrides, a strategy has been employed to improve the hydrogen isotope storage properties of ZrCo alloy which involves partial co-substitution of Zr with Ti and Nb. Herein, alloys of composition Zr_0.8Ti_0.2-xNb_xCo (x = 0.05, 0.1, 0.15) is prepared, characterized and the effect of Ti and Nb doping on hydrogen storage properties of parent ZrCo alloy is investigated. XRD analysis confirmed the formation of desired pure cubic phase of all the synthesized alloys similar to ZrCo phase. The presence of a single plateau in hydrogen desorption pressure-composition isotherms confirms single step hydrogen absorption-desorption behavior in Zr_0.8Ti_0.2-xNb_xCo alloys. The equilibrium pressure of hydrogen desorption decreases marginally with increasing Nb content in Zr_0.8Ti_0.2-xNb_xCo alloys which is further corroborated by differential scanning calorimetry measurements. Investigation of hydrogen induced disproportionation behavior in ITER-simulating condition revealed substantial impact of co-substitution of Ti and Nb on anti-disproportionation properties of ZrCo alloy. These remarkable properties make the Ti and Nb co-substituted quaternary alloys a desirable material for hydrogen isotope storage and delivery application.     

Improved hydrogen storage performance of the LiNH2–MgH2–LiBH4 system by addition of ZrCo hydride

Significant improvements in the hydrogen absorption/desorption properties of the 2LiNH₂–1.1MgH₂–0.1LiBH₄ composite have been achieved by adding 3wt% ZrCo hydride. The composite can absorb 5.3wt% hydrogen under 7.0 MPa hydrogen pressure in 10 min and desorb 3.75wt% hydrogen under 0.1 MPa H₂ pressure in 60 min at 150 °C, compared with 2.75wt% and 1.67wt% hydrogen under the same hydrogenation/dehydrogenation conditions without the ZrCo hydride addition, respectively. TPD measurements showed that the dehydrogenation temperature of the ZrCo hydride-doped sample was decreased about 10 °C compared to that of the pristine sample. It is concluded that both the homogeneous distribution of ZrCo particles in the matrix observed by SEM and EDS and the destabilized N–H bonds detected by IR spectrum are the main reasons for the improvement of H-cycling kinetics of the 2LiNH₂–1.1MgH₂–0.1LiBH₄ system.     

Band gap engineering in ruthenium‐based Heusler alloys for thermoelectric applications

In this work, systematic electronic structure calculations are performed on Ru₂TiZ alloys to examine their structural and thermoelectric related transport properties. The electronic structural properties are analyzed using the GGA and GGA+U as exchange correlational potential. The calculated lattice parameters agree very well with the existing experimental data, and the percentage of error is less than 1%. The electronic structural properties as analyzed, using the GGA exchange correlation scheme, reveal that these alloys can be semimetals. In the band structure, it is observed that ruthenium‐d and titanium‐d states are lying very close to the Fermi level. Hence, computations are performed again by including the Hubbard potential for d states of ruthenium and titanium. The calculated electronic structure in GGA+U reveals that all the 3 alloys are semiconductors with the indirect energy gap of 0.209, 0.175, and 0.259 eV, respectively, for Ru₂TiSi, Ru₂TiGe, and Ru₂TiSn. The electrical transport coefficients are calculated in both the GGA and GGA+U exchange correlational potential and reported. If experimentalists prove that these alloys are semiconductors, then all 3 alloys will be potential thermoelectric materials. If by experiment they are semimetals, only then Ru₂TiSn can be a good thermoelectric material. Doping of electron and hole for various concentrations is studied for Ru₂TiSn, and optimum doping level is reported.     

Enhanced thermodynamic properties of ZrNiH3 by substitution with transition metals (V,Ti, Fe,Mn and Cr)

First-principles calculations based on Plane-Wave Self-Consistent Field (PWSCF) method, implemented in quantum espresso program, have been performed on ZrNiH₃ substituted with transition metals (V, Ti, Fe, Mn, and Cr). The study aims to investigate the heat of formation in terms of material stability and desorption temperature. It is found that the substitution by transition metals, results in a significant enhancement in the thermodynamic properties accompanied by an increase of the volumetric and gravimetric hydrogen storage capacities. In addition, the obtained values of heat of formation and desorption temperature corroborate with that required by the U.S. Department of Energy (DOE) for stability and volumetric capacity criteria. Moreover, Mn and Fe elements are found to present the lowest substituting content (34%) to obtain optimum hydrogen storage characteristics (enthalpy of formation of - 40 kJ/mol.H₂, decomposition temperature of 300 K and volumetric capacity of 134 g.H₂/l), without affecting the electronic structure and the metallic character of ZrNiH₃.     

Dynamical stability of the lanthanum dihydride under high pressure: A density functional lattice dynamics approach

We report first-principles pseudopotential method and density functional linear response theory calculations of the structural, electronic, vibrational and thermodynamical properties of LaH₂ in fluoride phase at zero and high pressures. The electronic band structure and first time calculated pressure dependent lattice dynamic properties show that the LaH₂ is metallic in nature at zero pressure. The pressure dependent electronic band structure calculations show that the bands are closing and reopening with pressure. The phonon mode softens at 11 GPa indicating an instability in lattice structure and pressure induced transverse acoustic phonon mode driven displacive type structural phase transition. The LaH₂ also shows weak superconductivity at zero pressure. The valence charge electron density at 46 GPa shows a cage type charge contour and a space where hydrogen can be absorbed and filled easily. There is a considerable charge accumulation in the bonding region of La and H atoms, which strengthens covalent character of LaH₂, and henceforth this material can be one of the best materials for hydrogen storage application at high pressures.     

Electronic structure and phase stability of plutonium hydrides: Role of Coulomb repulsion and spin-orbital coupling

The electronic and magnetic states, chemical bonding and reactions, and phonon spectrum of the plutonium hydrides PuH_x (x = 2, 3) are investigated by employing first-principles calculations by means of the density functional theory (DFT) + U approach. The strong correlation and the spin-orbit coupling (SOC) effects on these 5f electrons systems are systematically studied. Results show that both the strong correlation and the SOC play critical roles in correctly describing their ground-state properties. The antiferromagnetic configuration of PuH₂ is found energetically most stable while for PuH₃ the ferromagnetic state is the most stable state. Our calculated phonon spectra clearly indicate the dynamical stability of these magnetic configurations. For PuH₃, more electrons from the Pu atoms are released to bond with H than that in PuH₂. As a result, the lattice constant is contracted by increasing the H concentration. Reacting from metal Pu and molecule H₂, more PuH₃ should be produced than PuH₂ in low temperature condition.