Reversible hydrogen-storage functions for mixtures of Li3N and Mg3N2

The hydriding and dehydriding reactions occurring in mixtures of lithium and magnesium nitrides (Li₃N and Mg₃N₂) were investigated for the first time in fixed composition ratios. A mixture of Li₃N–20 at.%Mg₃N₂ after heat treatment at 833 K was hydrogenated at 523 K in 35 MPa according to the following overall reaction: 4Li₃N+Mg₃N₂+12H₂ 12LiH+3Mg(NH₂)₂. This reaction is one of the candidates for reversible hydrogen-storage functions in which 9.1 mass% of hydrogen can be stored in the solid state. PACS 81.05.Zx; 71.20.Ps; 82.30.-b     

Energy bands of and spinwave dispersion in Pd3Fe

The results of a band calculation carried out for ferromagnetic Pd₃Fe suggest that the anisotropy observed in the spinwave dispersion curves may be explained by the particular shapes of the upspin and downspin Fermi surfaces and the symmetries of the corresponding one-electron states. The specific number of outer electrons per unit cell seems important in producing a Fermi level in a trough in the density of states so that only few states are involved. Qualitative considerations along the same lines seem capable of explaining differences in the spinwave dispersion of Pt₃Mn compared with that of Pd₃Fe.     

Chemical bonding and lithium ion conductions in Li3N

Electronic states of Li ions during the ionic jumps in the Li₃N crystal was discussed on the basis of the first principle molecular orbital calculations. The movements of the Li ions were simulated by several model clusters with different positions of the moving cation. The net charge of the moving Li ion and the total bond overlap population between the moving Li ion and the other ions were used for discussion of chemical bonding of the moving Li ion. Furthermore we have estimated the local cluster energy (LCE) to compare the energy change in the different moving path of the Li ion. The total bond overlap population of the moving Li ion along the conduction path changed smaller than those of the other paths. On the other hand, the changes of the net charges of the moving Li ions were similar in any paths. The change of the LCE in the model cluster of the conduction path was much smaller than that in another model cluster. As the results, the smaller change of the total bond overlap population of the moving Li ions played an important role for the fast ion movement in the Li ion conductors, rather than the change of the net charge of the moving Li ions. This bonding state of the moving Li ions is one of the characteristics of the electronic state in Li ion conductors.     

Cusp values and electron densities at coalescence

The correlation between errors in (a) calculated cusp values and (b) calculated electron densities at coalescence are examined for the electron-nucleus and electron-electron pairs in helium. Calculations for 25 fully optimized variational wavefunctions for the ground state are presented. Although a wide variety of functional forms are represented in the set of wavefunctions studied, a strong correlation between (a) and (b) is obtained in the case of the electron-nucleus pair, and a weaker but still significant correlation is found for the electron-electron pair.     

Energy bands: Chern numbers and symmetry

Energy bands formed by rotation–vibrational states of molecules in the presence of symmetry and their qualitative modifications under variation of some control parameters are studied within the semi-quantum model. Rotational variables are treated as classical whereas a finite set of vibrational states is considered as quantum. In the two-state approximation the system is described in terms of a fiber bundle with the base space being a two-dimensional sphere, the classical phase space for rotational variables. Generically this rank 2 complex vector bundle can be decomposed into two complex line bundles characterized by a topological invariant, the first Chern class. A general method of explicit calculation of Chern classes and of their possible modifications under variation of control parameters in the presence of symmetry is suggested. The construction of iso-Chern diagrams which split the space of control parameters into connected domains with fixed Chern numbers is suggested. A detailed analysis of the rovibrational model Hamiltonian for a D₃ invariant molecule possessing two vibrational states transforming according to the two-dimensional irreducible representation is done to illustrate non-trivial restrictions imposed by symmetry on possible values of Chern classes.     

β-Radiation Detected Li Diffusion in the Fast Ionic Conductor Li3N

The method of β-radiation detected nuclear magnetic resonance (β-NMR) was applied to ⁸Li in a ⁷Li₃N single crystal. From NMR signals and spin-lattice relaxation rates the activation enthalpies for two distinct Li⁺ diffusion processes were deduced. Ultraslow diffusion corresponding to ionic jump rates down to 0.1 s^?1 was observed. It could be confirmed that the static electric field gradients at the two inequivalent Li sites have opposite signs.     

The gas phase infrared band contours of s-triazine and s-triazine-d3: The fundamentals of C3N3H3 and C3N3D3 and some overtone and combination bands of C3N3H3

The systematic application of band contour techniques to account for most of the observed features of the ir spectra of s-triazine and s-triazine-d₃ have been made as well as a critique as to the limitations of such methods. The experimental and computer methods used to study the gas phase infrared band contours of s-triazine and s-triazine-d₃ are out-lined. Contours of the five E′ fundamentals of s-triazine have been recorded under moderate resolution and analyzed to give the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$, i = 6–10. The effects of l-resonance are very apparent for ν₈ and ν₉, in the form of holes in the Q branches of these bands. Under the highest resolution available, ν₆ and ν₁₀ also show l-resonance effects. Values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ were obtained for these four fundamentals. One of the parallel A₂″ fundamentals of C₃H₃N₃ (ν₁₂) has also been studied. It lies close to ν₁₀(E′) and an A × E type of second-order Coriolis resonance may be the cause of the intensity enhancement observed in the inner wings of the ν₁₂ and ν₁₀ bands. Hot bands of the type (ν_i + nν₁₄ ? nν₁₄) have been observed in the contours of ν₈, ν₁₀, and ν₁₂. This is felt to be responsible for the large difference between our observed zeta sum (?1.30) and the theoretical sum (?1.00).The gas phase infrared band contours of the five E′ and 2A₂″ fundamentals of C₃N₃D₃ have also been recorded under moderate resolution. From P-R separations and by computer simulation of the contours, values of the Coriolis constants $\text{ζ}{}_{\mathrm{i}}{}^{\mathrm{z}}$ have been obtained for the E′ modes. The effects of l-resonance have been observed for ν₈(E′) and ν₁₀(E′) and values of the l-doubling constants $\text{q}{}_{\mathrm{i}}{}^{\mathrm{(+)}}$ have been estimated. An extensive series of hot bands of the type (ν₁₂ + nν₁₄ ? nν₁₄) has been observed in the contour of the ν₁₂ (A₂″) fundamental. The mass effect on the Coriolis constants has been discussed.Infrared band contours of the overtone 2ν₇ and seven degenerate E′ combination bands of C₃N₃H₃ have been recorded under moderate resolution. Analysis of these contours using the P-R separation method and computer simulation of the contours has given values of $\text{ζ}{}_{\mathrm{<mtext>eff</mtext>}}{}^{\mathrm{z}}$ for these bands. Fermi resonance between 2ν₇ and ν₆ has been analyzed. The importance of considering both the observed contour as well as the observed frequency when assigning higher tone bands is illustrated.     

Energy bands of LaAg and LaCd and martensitic transformation

Energy bands of the simple cubic intermetallic compounds LaAg and LaCd have been calculated by using both a non-relativistic APW and relativistic KKR method in the muffin-tin-potential approximation. The density of states of LaAg is found to peak sharply just above the Fermi energy and the Fermi surface geometry shows that in this high density-of-states region the conditions are met for the band-Jahn-Teller-effect to drive the martensitic transformation observed in LaAg_{1_x} In _x ,x >0.05, and in LaCd. The case of YZn, which shows no martensitic transformation, is discussed briefly.     

New cubic phase of Li3N: stability of the N3- ion to 200 GPa

Diamond-anvil cell experiments augmented by first-principles calculations have found a remarkable stability of the N(3-) ion in Li3N to a sixfold volume reduction. A new (gamma) phase is discovered above 40(+/-5) GPa, with an 8% volume collapse and a band gap quadrupling at the transition determined by synchrotron x-ray diffraction and inelastic x-ray scattering. gamma-Li(3)N (Fm3m, Li(3)Bi-like structure) remains stable up to 200 GPa, and calculations do not predict metallization until approximately 8 TPa. The high structural stability, wide band gap, and simple electronic structure make this N(3-) based system analogous to lower valency compounds (MgO, NaCl, Ne), meriting its use as an internal pressure standard.     

Image of electron densities from line and plane projections

We compare Fourier transforms with orthogonal polynomials techniques applied in reconstructing three-dimensional electron–positron momentum densities from two-dimensional angular correlation of annihilation radiation (2D-ACAR) spectra and electron momentum densities from one-dimensional Compton profiles (1D-CP). In the case of Fourier transforms, we show results for two different algorithms: filtered back projection and Fourier–Bessel method. These techniques are presented for 2D-ACAR spectra in Y, ErGa₃ and model profiles. PACS 78.70.Bj; 87.59.Fm; 71.18.+y     

Accuracy of topological analysis of gridded electron densities

Topological analysis of electron densities sampled on 3D grids have been performed on two different crystalline compounds—ammonium dihydrogen phosphate and urea—using the software package InteGriTy and the results are compared to that of analytical derivation from the software Newprop and TOPOND. Both critical points and integrated quantities are considered with emphasis put on bond critical points and atomic charges.     

Formation Mechanism and Binding Energy for Equilateral Triangle Structure of Li3 Cluster

The formation mechanism for the equilateral triangle structure of Li3 cluster is proposed. The curve of the total energy versus the interatomic distance for this structure has been calculated by using the method of Gou‘s Modified Arrangement Channel Quantum Mechanics. The result shows that the curve has a minimal energy of-22.338 60 a.u at R = 5.82 a0. The total energy of Li3 when R approaches ∞ has the value of-22.284 09 a.u. This is also the total energy of three lithium atoms dissociated from Li3. The difference value of 0.0545 08 a.u. for the above two energy values is the dissociation energy of Li3 cluster, which is also its binding energy. Therefore the binding energy per lithium atom for Li3 is 0.018 169 a.u. = 0.494 eV, which is greater than the binding energy of 0.453 eV per atom for Li2 calculated in a previous work. This means that the Li3 cluster may be formed in the equilateral triangle structure of side length R = 5.82a0 stably with a stronger binding from the symmetrical interaction among the three lithium atoms.     

Nα and N6Li microscopic potentials

The nucleon-alpha and nucleon-lithium potentials are generated from Green's density dependent effective nucleon-nucleon interaction using a microscopic model with antisymmetrization effects included. A phenomenological parametrization and the energy dependence of the potentials are derived.     

On effective electron mass of silicon field structures at low electron densities

The trial wave function method developed in [10, 11] for the case of a narrow s band in a perfect crystal is adapted for the calculation of the concentration dependence of the effective mass and the Landé factor in a two-dimensional electron system of low density. It has been found that the effective mass has a tendency to divergence at a certain critical concentration, whereas the g factor remains finite.     

Stopping of ions and local electron densities at strong coupling

We employ molecular dynamics (MD) computer simulations to investigate ions in electron plasmas at strong coupling. We observed in this regime a stopping power of highly charged ions at low velocities which scales with the charge like Z^1.5. This clearly deviates from the Z² ln(const./Z) scaling of the conventional weak coupling theories and is connected with a strongly enhanced local density of electrons around the ions which is caused by the trapping of electrons in high Rydberg states due to multi-particle collisions occurring at strong coupling. For the parameters corresponding to the less strongly coupled situation in an electron cooler we find a moderate enhancement of the local electron density created under the influence of the external magnetic field. This revised version was published online in August 2006 with corrections to the Cover Date.     

Yrast bands in N = 91 isotones

The in-beam spectroscopy on N = 91 isotones has been carried out using the ¹²C + ¹⁵⁰Nd reaction. The νi _13/2 and νh _11/2 bands of ¹⁵³Sm have been extended up to 33/2⁺ and 31/2^-, respectively. Two new γ-rays have been located on the top of the unfavored band with νi _13/2 configuration in ¹⁵⁷Dy. Two identical relationships have been established in the low-spin region of the yrast νi _13/2 configuration between ¹⁵³Sm and ¹⁵⁵Gd, and between unfavored bands of ¹⁵⁵Gd and ¹⁵⁷Dy. Here all these nuclei have the same neutron number N = 91. Received: 28 June 2000 / Accepted: 20 October 2000     

Synthesis of Cubic Boron Nitride by the Reaction of Li3N and B2O3

Cubic boron nitride is synthesized by the reaction of Li3N and B203 under high pressure and high temperature （4.0-5.0 GPa, 1350-1500℃）. The minimum pressure of cBN formation is 4.0 GPa. The present condition of cBN formation is clearly lower than the eutectic temperature of Li3BN2 and BN in the Li3N-hBN system （5.5 GPa, 1610℃）. The content of cBN in the sample increases, while the content of hBN decreases with the temperature and pressure. The maximum conversion rate （5.0 GPa, 1500℃） is about 34%, which is higher than that in the hBN-Li3N system. The cBN crystals are octahedral or tetrahedral in shape and approximately 20 μm in diameter.