86 research outputs found
Electronic structure, phase stability and chemical bonding in ThAl and ThAlH
We present the results of theoretical investigation on the electronic
structure, bonding nature and ground state properties of ThAl and
ThAlH using generalized-gradient-corrected first-principles
full-potential density-functional calculations. ThAlH has been reported
to violate the "2 \AA rule" of H-H separation in hydrides. From our total
energy as well as force-minimization calculations, we found a shortest H-H
separation of 1.95 {\AA} in accordance with recent high resolution powder
neutron diffraction experiments. When the ThAl matrix is hydrogenated, the
volume expansion is highly anisotropic, which is quite opposite to other
hydrides having the same crystal structure. The bonding nature of these
materials are analyzed from the density of states, crystal-orbital Hamiltonian
population and valence-charge-density analyses. Our calculation predicts
different nature of bonding for the H atoms along and . The strongest
bonding in ThAlH is between Th and H along which form dumb-bell
shaped H-Th-H subunits. Due to this strong covalent interaction there is very
small amount of electrons present between H atoms along which makes
repulsive interaction between the H atoms smaller and this is the precise
reason why the 2 {\AA} rule is violated. The large difference in the
interatomic distances between the interstitial region where one can accommodate
H in the and planes along with the strong covalent interaction
between Th and H are the main reasons for highly anisotropic volume expansion
on hydrogenation of ThAl.Comment: 14 pages, 9 figure
Theory for Metal Hydrides with Switchable Optical Properties
Recently it has been discovered that lanthanum, yttrium, and other metal
hydride films show dramatic changes in the optical properties at the
metal-insulator transition. Such changes on a high energy scale suggest the
electronic structure is best described by a local model based on negatively
charged hydrogen (H) ions. We develop a many-body theory for the strong
correlation in a H ion lattice. The metal hydride is described by a large
-limit of an Anderson lattice model. We use lanthanum hydride as a prototype
of these compounds, and find LaH is an insulator with a substantial gap
consistent with experiments. It may be viewed either as a Kondo insulator or a
band insulator due to strong electron correlation. A H vacancy state in LaH
is found to be highly localized due to the strong bonding between the electron
orbitals of hydrogen and metal atoms. Unlike the impurity states in the usual
semiconductors, there is only weak internal optical transitions within the
vacancy. The metal-insulator transition takes place in a band of these vacancy
states.Comment: 18 pages, 16 figures and 6 tables. Submitted to PR
Isotope effects in switchable metal-hydride mirrors
Measurements of optical reflectance, transmittance, and electrical resistivity on the switchable mirror systems YHx and YDx show that the absorption of hydrogen induces the same variations as that of deuterium. In both cases there is a weak transparency window for the metallic dihydride (dideuteride) phase and a yellowish transparency in the insulating trihydride (trideuteride) phase. The slightly higher electrical resistivity of the deuterides is related to the lower energy of their optical phonons. The absence of significant isotope effects in the optical properties of YHx(YDx) is at variance with Peierls-like theoretical models. It is, however, compatible with strong electron correlation model
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