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Ulrich Häussermann

Publications and source records attributed to Ulrich Häussermann.

14 recordsLinked to original sources
PubMed2006

Polyanionic hydrides from polar intermetallics AeE2 (Ae = Ca, Sr, Ba; E = Al, Ga, In).

The hydrogenation behavior of the polar intermetallic systems AeE2 (Ae = Ca, Sr, Ba; E = Al, Ga, In) has been investigated systematically and afforded the new hydrides SrGa2H2 and BaGa2H2. The structure of these hydrides was characterized by X-ray powder diffraction and neutron diffraction of the corresponding deuterides. Both compounds are isostructural to previously discovered SrAl2H2 (space group P3m1, Z = 1, SrGa2H2/D2: a = 4.4010(4)/4.3932(8) A, c = 4.7109(4)/4.699(1) A; BaGa2H2/D2: a = 4.5334(6)/4.5286(5) A, c = 4.9069(9)/4.8991(9) A). The three hydrides SrAl2H2, SrGa2H2, and BaGa2H2 decompose at around 300 degrees C at atmospheric pressure. First-principles electronic structure calculations reveal that H is unambiguously part of a two-dimensional polyanion [E2H2]2- in which each E atom is tetrahedrally coordinated by three additional E atoms and H. The compounds AeE2H2 are classified as polyanionic hydrides. The peculiar feature of polyanionic hydrides is the incorporation of H in a polymeric anion where it acts as a terminating ligand. Polyanionic hydrides provide unprecedented arrangements with both E-E and E-H bonds. The hydrogenation of AeE2 to AeE2H2 takes place at low reaction temperatures (around 200 degrees C), which suggests that the polyanion of the polar intermetallics ([E2]2-) is employed as precursor.

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PubMed2005

KBi(2-x)Pbx (0 < x <or= 1): a Zintl phase evolving from a distortion of the cubic Laves-phase structure.

The quasibinary system KBi(2-x)Pbx has been investigated, both experimentally and theoretically. Phases with compositions 0 < or = x < or = 1.2 were synthesized and structurally characterized by X-ray diffraction experiments. For low values of x (0 < or = x < 0.6), KBi(2-x)Pbx adopts the cubic Laves-phase structure MgCu2 (space group Fdm), which contains a rigid framework of corner-condensed symmetry-equivalent tetrahedra formed by randomly distributed Bi and Pb atoms. For compositions x > or = 0.6, these tetrahedra become alternately elongated and contracted. The distortion of the framework lowers the space-group symmetry to F43m (KBi(1.2)Pb(0.8), F43m, Z = 8, a = 9.572(1) A). Magnetometer measurements show that KBi2 (x = 0) is metallic and goes through a superconducting transition below 3.5 K. First principles calculations reveal that the Fd3m --> F43m distortion is largest for KBiPb (x = 1.0), which at the same time turns into a semiconductor. Thus, F43m KBiPb corresponds to a proper charge-balanced Zintl phase, K+[BiPb]-, with separated polyanionic tetrahedra, (Bi2Pb2)2-. However, it was not possible to prepare F43m KBiPb. Syntheses attempting to increase the Pb content in KBi(2-x)Pbx above x = 0.8 yielded additional, not yet characterized, ternary phases.

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PubMed2005

Structure and bonding of zinc antimonides: complex frameworks and narrow band gaps.

We investigated crystal structure relationships, phase stability and chemical bonding of the thermoelectric materials ZnSb, alpha-Zn4Sb3, and beta-Zn4Sb3 by means of first principles calculations. The structures of these materials are difficult to rationalise. This is especially true for beta-Zn4Sb3 because of the presence of vacancies and interstitial atoms. We recognised rhomboid rings Zn2Sb2 as central structural building units present in all materials. Importantly, these rings enable to establish a clear relationship between disordered beta-Zn4Sb3 and ordered low-temperature alpha-Zn4Sb3. Concerning the phase stability of Zn4Sb3 we identified a peculiar situation: alpha-Zn4Sb3 is metastable and beta-Zn4Sb3 can only be thermodynamically stable when its structural disorder accounts for a large entropy contribution to free energy. According to their electronic structure zinc antimonides represent heteroatomic framework structures with a modest polarity. The peculiar electronic structure of Zn/Sb systems can also be modelled by Al/Si systems. The high coordination numbers in the frameworks implies the presence of multicentre bonding. We developed a simple bonding picture for these frameworks where multicentre bonding is confined to rhomboid rings Zn2Sb2.

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PubMed2004

The structure of alpha-Zn4Sb3: ordering of the phonon-glass thermoelectric material beta-Zn4Sb3.

beta-Zn4Sb3 is an outstanding thermoelectric material mainly due to its extraordinarily low thermal conductivity, which is similar to that of glasses. Recently it was proposed that interstitial Zn atoms are responsible for this peculiar behavior. Here we report on the crystal and electronic stucture of the low-temperature polymorph alpha-Zn4Sb3. During the reversible phase transition the intricate disorder in beta-Zn4Sb3 disappears, and all Zn atoms localize completely. The electronic structure of alpha-Zn4Sb3 corresponds to that of a narrow-gap semiconductor.

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PubMed2004

Phase stability in the systems AeAl(2-x)Mgx (Ae = Ca, Sr, Ba): electron concentration and size controlled variations on the laves phase structural theme.

The systems AeAl(2-x)Mgx (Ae = Ca, Sr, Ba) display electron concentration induced Laves phase structural changes. However, the complete sequence MgCu2 --> MgNi2 --> MgZn2 with increasing x (decreasing electron count) is only observed for Ae = Ca. Compounds SrAl(2-x)Mgx (0 < x < or = 2) and BaAl(2-x)Mgx (x = 0.85 and 2.0) were synthesized and structurally characterized by X-ray diffraction experiments. For the Sr system the structural sequence CeCu2 --> MgNi2 --> MgZn2 occurs with increasing Mg content x. Thus, larger Sr does not allow the realization of the MgCu2 structure at low x. For Ae = Ba a binary compound BaAl2 does not exist, but more Ba-rich Ba7Al13 forms. The reinvestigation of the crystal structure of Ba7Al13 by selected area and convergent beam electron diffraction in a transmission electron microscope revealed a superstructure, which subsequently could be refined from single X-ray diffraction data. The formula unit of the superstructure is Ba21Al40 (space group P31m, Z = 1, a = 10.568(1) angstroms, c = 17.205(6) angstroms). In Ba21Al40 a size match problem between Ba and Al present in Ba7Al13 is resolved. The structure of Ba7Al13 (Ba21Al40) can be considered as a Ba excess variant of the hexagonal MgNi2 Laves phase type structure. An incommensurately modulated variant of the MgNi2 structure is obtained for phases BaAl(2-x)Mgx with x = 0.8-1. At even higher Mg concentrations a structural change to the proper MgZn2 type structure takes place.

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PubMed2003

Structure and bonding of Sr3In11: how size and electronic effects determine structural stability of polar intermetallic compounds.

The binary compound Sr(3)In(11) (SrIn(3.667)) was synthesized and structurally characterized by X-ray diffraction experiments. It crystallizes in the orthorhombic La(3)Al(11) structure type (space group Immm, Z = 2; a = 4.9257(6), b = 14.247(2), c = 11.212(2) A). The crystal structure of Sr(3)In(11) bears features of the monoclinic EuIn(4) structure, which is adopted by SrIn(4), and the prominent tetragonal BaAl(4) structure. Sr(3)In(11) is stable until 550 degrees C. At higher temperatures it decomposes peritectically into SrIn(2) and In. Structural stability and bonding properties of Sr(3)In(11) were investigated by first principles calculations and compared to SrIn(4) in the monoclinic EuIn(4) and the tetragonal BaAl(4) structure. All three structures consist of a three-dimensional, polyanionic, network formed by In atoms and Sr cations encapsulated in cages. For the BaAl(4)-type SrIn(4), In-In network bonding is perfectly optimized. In contrast, the networks of EuIn(4)-type SrIn(4) and Sr(3)In(11) appear hypo- and hyperelectronic, respectively. The formation of Sr(3)In(11) with a composition close to 1:4 and the nonexistence of BaAl(4)-type SrIn(4) is explained by a delicate interplay of size and electronic factors governing structural stability in the In-rich part of the Sr-In system.

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PubMed2003

High-pressure structural trends of Group 15 elements: simple packed structures versus complex host-guest arrangements.

The Group 15 elements P, As, Sb, and Bi all have layered structures consisting of six-membered rings under ambient conditions and attain the body-centered cubic (bcc) structure at the highest pressures applied. In the intermediate pressure region, however, phosphorus and its heavier congeners behave profoundly differently. In this region P first attains the open packed simple cubic (sc) structure for a wide range of pressures and then transforms into the rarely observed simple hexagonal (sh) structure. For the heavier congeners complex, incommensurately modulated host-guest structures emerge as intermediate pressure structures. We investigated the high-pressure behavior of P and As by ab initio density functional calculations in which pseudopotentials and a plane wave basis set were employed. The incommensurately modulated high-pressure structure of As was approximated by a supercell. Our calculations reproduced the experimentally established pressure stability ranges of the sc and sh structures for P and the host-guest structure for As very well. We found that the sc and especially the sh structure are decisively stabilized by the admixture of d states in the occupied levels of the electronic structure. This admixture releases s-s antibonding states above the Fermi level (s-d mixing). With pressure, s-d mixing increases rapidly for P, whereas it remains at a low level for As. As a consequence, the band energy contribution to the total energy determines the structural stability for P in the intermediate pressure region, giving rise to simple packed structures. On the other hand, in the intermediate pressure region of the heavier Group 15 elements, a delicate interplay between the electrostatic Madelung energy and the band energy leads to the formation of complex structures.

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PubMed2003

Laves-phase structural changes in the system CaAl2-xMgx.

Compounds CaAl(2)(-)(x)Mg(x) (0 < or = x < or = 2) were synthesized and structurally characterized by X-ray diffraction experiments. With increasing Mg content x the sequence of Laves phase structures MgCu(2) --> MgNi(2) --> MgZn(2) is revealed. The homogeneity ranges of the underlying phases were determined to be 0 < or = x < 0.24(1) (MgCu(2) type), 0.66(2) < x < 1.07(3) (MgNi(2) type), and 1.51(5) < x < or = 2.0 (MgZn(2) type). Mg/Al site occupancies in CaAl(1.34)Mg(0.66) and in CaAl(0.44)Mg(1.56) were refined from neutron powder diffraction experiments and exposed a pronounced segregation of Al and Mg in MgNi(2)-type CaAl(1.34)Mg(0.66) where Al atoms preferentially occupy the positions corresponding to trigonal bipyramids. In MgZn(2)-type CaAl(0.44)Mg(1.56), however, the Mg/Al distribution was found to be nearly uniform. Structural stability in the quasi-binary system CaAl(2)(-)(x)Mg(x) was investigated by first-principles calculations in which random occupational disorder of Mg and Al was modeled with the virtual crystal approximation. The theoretical calculations reproduced the experimental compositional stability ranges of the three different Laves phase structures very well. Structural changes in the quasi-binary system CaAl(2)(-)(x)Mg(x) are induced by the electron concentration, which decreases with increasing x. The stability of the different Laves phase structures as a function of electron concentration was analyzed by the method of moments.

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PubMed2002

Comparative study of the high-pressure behavior of As, Sb, and Bi.

The high-pressure behavior of the heavier group 15 elements As, Sb, and Bi was investigated by means of ab initio density functional calculations employing pseudopotentials and a plane wave basis set. The high-pressure structural sequence of these elements is distinguished by the occurrence of the Bi-III structure, which is a complex, incommensurately modulated, host-guest structure. We approximated this structure by a supercell which reproduced the experimentally established pressure stability ranges of the host-guest structure for the different elements extremely well. With pressure we find an increasing admixture of d states (s-d hybridization) in the occupied levels of the electronic structure of As, Sb, and Bi. However, the s-d mixing remains at a low level. Thus, the emergence of a complex intermediate pressure structure cannot be explained by a pressure-induced altered valence state for these elements. Instead, it is argued that the Bi-III structure is a consequence of a delicate interplay between the electrostatic and the band energy contribution to the total energy. In the intermediate pressure range of heavier group 15 elements, both important parts of the total energy account equally for structural stability.

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PubMed2002

Bonding and stability of the hydrogen storage material Mg(2)NiH(4).

Structural stability and bonding properties of the hydrogen storage material Mg(2)NiH(4) (monoclinic, C2/c, Z = 8) were investigated and compared to those of Ba(2)PdH(4) (orthorhombic, Pnma, Z = 8) using ab initio density functional calculations. Both compounds belong to the family of complex transition metal hydrides. Their crystal structures contain discrete tetrahedral 18 electron complexes T(0)H(4)(4-) (T = Ni, Pd). However, the bonding situation in the two systems was found to be quite different. For Ba(2)PdH(4), the electronic density of states mirrors perfectly the molecular states of the complex PdH(4)(4-), whereas for Mg(2)NiH(4) a clear relation between molecular states of TH(4)(4-) and the density of states of the solid-state compound is missing. Differences in bonding of Ba(2)PdH(4) and Mg(2)NiH(4) originate in the different strength of the T-H interactions (Pd[bond]H interactions are considerably stronger than Ni[bond]H ones) and in the different strength of the interaction between the alkaline-earth metal component and H (Ba[bond]H interactions are substantially weaker than Mg[bond]H ones). To lower the hydrogen desorption temperature of Mg(2)NiH(4), it is suggested to destabilize this compound by introducing defects in the counterion matrix surrounding the tetrahedral Ni(0)H(4)(4-) complexes. This might be achieved by substituting Mg for Al.

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PubMed2002

The s-p bonded representatives of the prominent BaAl4 structure type: a case study on structural stability of polar intermetallic network structures.

This work presents a detailed, combined experimental and theoretical study on the structural stability of s-p bonded compounds with the BaAl4 structure type (space group I4/mmm, Z = 2) as part of a broad program to investigate the complex questions of structure formation and atomic arrangements in polar intermetallics. From ab initio calculations employing pseudopotentials and a plane wave basis set, we extracted optimized structural parameters, binding energies, and the electronic structure of the systems AeX(III)4, AeX(II)2X(IV)2, AeX(II)2X(III)2 (Ae = Ca, Sr, Ba; X(II) = Mg, Zn; X(III) = Al, Ga; X(IV) = Si, Ge). For all systems we found a pronounced pseudo-gap in the density of states separating network X42- bonding from antibonding electronic states that coincides with the Fermi level for an electron count of 14 electrons per formula unit, the optimum value for stable BaAl4-type polar intermetallics. However, the synthesis and structural characterization (from X-ray single crystal and powder diffraction data) of the new compounds AeZn2-Al2+, AeZn2-deltaGa2+delta (Ae = Ca, Sr, Ba; delta = 0-0.2) and AeMg0.9Al3.1, AeMg1.7Ga2.3 (Ae = Sr, Ba) manifested that electron deficiency is rather frequent for BaAl4-type polar intermetallics. The site preference for different "X" elements in the ternary systems was quantified by calculating "coloring energies", which, for some systems, was strongly dependent on the size of the electropositive Ae component. The Ae2+ cations decisively influence the nearest neighbor distances in the encapsulating polyanionic networks X4(2-) and the structures of these networks are surprisingly flexible to the size of the Ae component without changing the overall bonding picture. A monoclinically distorted variant of the BaAl4 structure occurs when the cations become too small for matching the size of encapsulating X4(2-) cages. An even larger size mismatch leads to the formation of the EuIn4 structure type.

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PubMed1997

The Phase Co(1)(-)(x)()Ni(x)()Sn(2): Structural Variations Based on the Stacking of Two Different Planar Nets.

The investigation of the tin-rich part of the ternary system Co/Ni/Sn yielded the phase Co(1)(-)(x)()Ni(x)()Sn(2) with the range of composition 0.23(3) < x < 0.59(3). When using a large excess of tin, Co(1)(-)(x)()Ni(x)()Sn(2) crystallizes at 500 degrees C in a structure isotypic to that of tetragonal PdSn(2) whereas a modification with the orthorhombic CoGe(2) structure type always forms from a stoichiometric mixture of the elemental components or from a tin melt at temperatures above 550 degrees C. The structures of Co(0.625)Ni(0.375)Sn(2) were determined by single-crystal X-ray diffraction methods (PdSn(2)-type space group I4(1)/acd, a = 6.2360(5) Å, c = 23.588(2) Å, Z = 16; CoGe(2)-type space group Aba2, a = 6.2439(4) Å, b = 6.2493(4) Å, c = 11.778(1) Å, Z = 8). Both structures have the same building unit consisting of three consecutive planar nets 4(4), 3(2)434, 4(4) formed by tin atoms. The condensation of the building blocks in the c direction gives rise to different stacking sequences. In the PdSn(2)-type, a ABCD sequence is realized and the c axis is doubled compared to the ideal CoGe(2)-type with AB stacking. Electron diffraction and high-resolution electron microscopy studies revealed the existence of other, complex, stacking variants as well as stacking faults in the Co(1)(-)(x)()Ni(x)()Sn(2) system.

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