PdZn or ZnPd: Charge Transfer and Pd–Pd Bonding as the Driving Force for the Tetragonal Distortion of the Cubic Crystal Structure

The intermetallic compound PdZn was reported to have two modifications, the tetragonal CuAu-type low-temperature phase and the cubic CsCl-type high-temperature phase. The existence of the cubic high-temperature phase at the equiatomic composition could not be proven experimentally. Calculations of the total energy reveal a minimum at c/a = 1.155, clearly excluding the cubic structure at the equiatomic composition in the system Pd-Zn. Analysis of the chemical bonding applying the electron localizability approach reveals charge transfer from zinc to palladium and proves direct Pd–Pd interactions in the (001) plane to be the main reason for the tetragonal distortion of the cubic CsCl-type structural pattern for ZnPd.

[1]  R. Schlögl,et al.  Palladium–gallium intermetallic compounds for the selective hydrogenation of acetylene: Part I: Preparation and structural investigation under reaction conditions , 2008 .

[2]  Robert Schlögl,et al.  Palladium Gallium Intermetallic Compounds for the Selective Hydrogenation of Acetylene Part II: Surface Characterization and Catalytic Performance , 2008 .

[3]  M. Armbrüster,et al.  Chemical bonding in TiSb(2) and VSb(2): a quantum chemical and experimental study. , 2007, Inorganic chemistry.

[4]  Y. Grin,et al.  Charge decomposition analysis of the electron localizability indicator: a bridge between the orbital and direct space representation of the chemical bond. , 2007, Chemistry.

[5]  Konstantin M. Neyman,et al.  Microscopic models of PdZn alloy catalysts: structure and reactivity in methanol decomposition. , 2007, Physical chemistry chemical physics : PCCP.

[6]  R. Schlögl,et al.  A new approach to well-defined, stable and site-isolated catalysts , 2007 .

[7]  Y. Grin,et al.  Electron localization function in full-potential representation for crystalline materials. , 2006, The journal of physical chemistry. A.

[8]  A. Tsai,et al.  PdZn=Cu: Can an Intermetallic Compound Replace an Element? , 2004 .

[9]  Miroslav Kohout,et al.  Electron localization function for transition-metal compounds , 2002 .

[10]  Helmut Eschrig,et al.  FULL-POTENTIAL NONORTHOGONAL LOCAL-ORBITAL MINIMUM-BASIS BAND-STRUCTURE SCHEME , 1999 .

[11]  N. Iwasa,et al.  Steam reforming and dehydrogenation of methanol: Difference in the catalytic functions of copper and group VIII metals , 1997 .

[12]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[13]  B. Predel,et al.  Experimentelle Untersuchungen zur Struktur und Stabilität der Phase TiAl , 1995 .

[14]  A. Zunger,et al.  Comparison of experimental and theoretical electronic charge distribution in γ-TiAl , 1994 .

[15]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[16]  間庭 秀世,et al.  Max Hansen and Kurt Anderko: Constitution of Binary Alloys. McGraw-Hill Book Co., New York, 1958, 1305頁, 23×16cm, \13.000. , 1958 .

[17]  H. Nowotny,et al.  Ein Beitrag zum System Palladium-Zink , 1951 .

[18]  H. Nowotny,et al.  Die Kristallstruktur von PdZn , 1950 .

[19]  U. Dehlinger.  Zur Verformungsempfindlichkeit der metallischen Überstrukturen , 1937 .

[20]  Y. Grin,et al.  Spatial chemistry of the aluminium—platinum compounds: a quantum chemical approach , 2007 .

[21]  Y. Grin,et al.  Atomic Shells From the Electron Localizability in Momentum Space , 2006 .

[22]  Miroslav Kohout,et al.  A Measure of Electron Localizability , 2004 .

[23]  S. Ambler,et al.  THE ELEMENTS , 1998 .

[24]  R. Bader.  Atoms in molecules : a quantum theory , 1990 .

[25]  W. K. Wang,et al.  Isothermal compression of the L10-type alloy CuAu , 1987 .

[26]  Lawrence H. Bennett,et al.  Binary alloy phase diagrams , 1986 .

[27]  H. Ipser,et al.  The structural stability of the B2 and L10 phases in the system PdZn , 1978 .

[28]  T. S. Rao,et al.  Temperature and composition dependence of the elastic moduli of NiZn ferrites , 1978 .

[29]  C. H. Johansson,et al.  Röntgenographische Bestimmung der Atomanordnung in den Mischkristallreihen AuCu und PdCu , 1925 .