			Home About us Contact

Teller Distortion (teller + distortion)

Distribution by Scientific Domains

Chemistry	86%

Selected Abstracts

Minerals as Model Compounds for Cu/ZnO Catalyst Precursors: Structural and Thermal Properties and IR Spectra of Mineral and Synthetic (Zincian) Malachite, Rosasite and Aurichalcite and a Catalyst Precursor Mixture

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2009
Malte Behrens
Abstract The Cu/ZnO system is a model for Cu/ZnO/Al2O3 catalysts, which are employed industrially for the synthesis of methanol. These catalysts are usually prepared from mixed basic carbonate precursors. A complex phase mixture, with constituents structurally related to the minerals rosasite andaurichalcite, is present at the industrially applied composition (Cu/Zn , 70:30). Using minerals and phase-pure synthetic samples as references, a comprehensive characterisation of such a phase mixture, including the determination of the individual compositions of the different phases, has been attempted by complementary analytical laboratory techniques (XRD, TGA, IR). The results are critically discussed in light of the complexity of the system. A thermally very stable carbonate species , well-known for mixed synthetic systems , is also detected for the mineral reference samples. Significant amounts of amorphous phases are found to be present in the synthetic zincian malachite sample but not in synthetic aurichalcite or the catalyst precursor. A simplified explanation for the shift of the characteristic 20 reflection of the malachite structure as a function of Zn incorporation based on the varying average Jahn,Teller distortion of the MO6 octahedra is proposed. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]

Beyond the Icosahedron: A Density Functional Theory Study of 14-Atom Germanium Clusters

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 25 2008
R. Bruce King
Abstract Density functional theory (DFT) at the hybrid B3LYP level has been applied to the germanium clusters Ge14z (z = ,8, ,6, ,4, ,2, 0, +2, +4) starting from seven different initial configurations. An Oh omnicapped cube structure is the most stable for Ge142, followed by a hexagonal antiprism structure with a relative energy of 42.7 kcal/mol. The lowest-energy structure for neutral Ge14 is a triplet omnicapped cube with full Oh symmetry followed by a singlet omnicapped cube compressed to D4h symmetry through Jahn,Teller distortion. The lowest energy Ge142+ structure is also an Oh structure derived from the omnicapped cube through elongation of the 12 edges of the underlying cube to give a rhomboidal dodecahedron with 12 rhombus faces. The lowest-energy Ge124+ structure is a bicapped icosahedron. Some D6h hexagonal wheel structures at higher energies are also found for the hypoelectronic systems Ge14, Ge142+, and Ge144+. The lowest-energy structures for the hyperelectronic Ge144,, Ge146,, and Ge148, are relatively unsymmetrical not readily recognizable open structures typically with some pentagonal or hexagonal faces. The D6d bicapped hexagonal antiprism found in 14-vertex C2B12 carborane and M2C2B10 dimetallacarborane structures is not the lowest-energy structure for any of the Ge14z clusters.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Electron-Sponge Behavior, Reactivity and Electronic Structures of Cobalt-Centered Cubic Co9Te6(CO)8 Clusters

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2008
Mustapha Bencharif
Abstract Extended investigations of the reaction sequence [Cp,2Nb(Te2)H]/CH3Li/[Co2(CO)8] (Cp, = tBuC5H4) led to the identification of Lin[3] {3 = [Co9Te6(CO)8]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN]n[3] (PPN = Ph3PNPPh3). These compounds form in the solid state columnar ([PPN][3]) or undulated 2D ([PPN]2[3]) supramolecular networks. Electrochemical studies of [Cp*2Nb(CO)2][3] (Cp* = C5Me5) or [Na(THF)6][3] revealed the presence of the redox couples [3],/[3]2,/[3]3,/[3]4,/[3]5, regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [3], containing salts form with PPh3AuCl or dppe decomposition products like [(PPh3)2Au][CoCl3PPh3] or [Co(CO)2dppe]2(,-Te). A neutral cluster comprising the Co@Co8(,4 -Te)6 core formed in the reaction of [Cp*2Nb(CO)2][Co11Te7(CO)10] with PPh3AuCl, which gave [Co9Te6(CO)4(PPh3)4] (4) after oxidative cluster degradation and CO substitution. 4 was characterized by X-ray crystallography. DFT calculations carried out on all members of the [3]n (n = +1 to ,5) family and on related species indicate that there is no significant Jahn,Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][3] show that the ground state of [3], is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source]

Electronic spectra of [(CH3)2NH2]5Cd2CuCl11 crystals

PHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11 2004
V. Kapustianik
Abstract The temperature evolution of Cu2+ ion environment in the solid solutions of ((CH3)2NH2)5Cd2CuCl11 is studied on the basis of absorption spectroscopy data. For the detailed analysis of experimental data the special program package Crys Tool 1.0 based on quantum-mechanical models, first of all on the model of normalized spherical harmonics (NSH), has been employed. It has been found that similarly to the crystal of ((CH3)2NH2)5Cd3Cl11 (DMACC) the investigated solid solution contains tetragonally distorted octahedral metal,halogen complexes of two types and the degree of their distortion is changed considerably at the temperatures of phase transitions (PTs). The parameters of crystal field, angular overlap model, as well as the copper,chlorine distances, show continuous changes at T1 = 176 K that should be related to the second-order transition, whereas the jump-like anomalies of the spectral parameters at T2 = 115 K (on cooling) are characteristic of the first-order PTs. Introduction of the copper ions into the structure of the host DMACC crystal induces the shifts of these PTs toward low temperatures by 3.5 and 5 K, respectively. The observed structural changes around T0 = 313 K are connected with a complex co-operative effect involving weakening of the hydrogen bonds and modification of the Jahn,Teller distortion with temperature. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Exciton,phonon interaction and Raman spectra of [(CH3)2NH2]5Cd2CuCl11 crystals

PHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11 2004
V. Kapustianik
Abstract Temperature evolution of the exciton,phonon interaction (EPI) in ((CH3)2NH2)5Cd2CuCl11 solid solution was studied on the basis of absorption spectroscopy data. The obtained values of effective phonon energies were compared with the data of Raman spectroscopy. It is shown that the (T) and E, parameters of Urbach's rule show the continuous anomalous change characteristic of the second-order phase transition at T1 = 176 K. The anomalous behaviour of the EPI and other spectral parameters at T0 = 310,315 K was related to the complex co-operative effect involving weakening of the hydrogen bonds and variation of the Jahn,Teller distortion of metal,halogen polyhedra with temperature. This process takes place only within the copper,chlorine sublattice and due to this would be hardly related to the usual phase transition. At the same time, the considered temperature change of the tetragonal distortion of the metal,halogen octahedra is followed by nonfulfillment of Urbach's rule in the temperature range TT0. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Change in electronic structure in a six-coordinate copper(II) complex accompanied by an anion order/disorder transition

ACTA CRYSTALLOGRAPHICA SECTION B, Issue 2 2010
Colin A. Kilner
A variable-temperature crystallographic study of [Cu(LOH)2][ClO4]2·2(CH3)2CO [LOH = 2,6-bis(hydroxyiminomethyl)pyridine] between 30 and 300,K is presented. The complex exhibits an unusual electronic structure at room temperature with a {}1 ground state, corresponding to an axially compressed ligand coordination geometry about the copper ion. This reflects a suppression of the pseudo-Jahn,Teller distortion that is normally shown by copper(II) compounds with this ligand geometry [Halcrow et al. (2004). New J. Chem.28, 228,233]. On cooling the compound undergoes an abrupt structural change at 157,±,3,K, that does not involve a change in the space group (P), but causes significant changes to c and the unit-cell angles. This reflects a conformational rearrangement of the complex dication, towards a more typical pseudo-Jahn,Teller elongated coordination geometry. This occurs concurrently with a crystallographic ordering of one of the two perchlorate anions, and a significant displacement of the two lattice acetone molecules. The transformation involves displacements of up to 0.5,Å in the non-H atoms of the structure at 30,K, compared with their positions at 300,K. The change in coordination geometry of the complex around 157,K is reflected in a small reduction in its magnetic moment near that temperature. [source]

How to Build Molecules with Large Magnetic Anisotropy

CHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2009
Jordi Cirera Dr.
Abstract Predicting single-molecule magnets? Magnetic anisotropy, a property that plays a key role in single-molecule magnets (SMMs), has been analyzed by using theoretical methods. Mononuclear complexes and the dependence of the magnetic anisotropy on their geometrical and electronic structure, as well as how such mononuclear complexes must be combined as building blocks to obtain polynuclear complexes with large anisotropy (see figure) are considered. The magnetic anisotropy of mononuclear transition-metal complexes has been studied by means of electronic structure calculations based on density functional theory. The variation of the zero-field splitting (ZFS) parameters has been analyzed for the following characteristic distortions: a tetragonal Jahn,Teller distortion, the Bailar twist, the Berry pseudorotation, and the planarization of tetrahedral complexes. Finally, the coupling of mononuclear building blocks in polynuclear complexes to obtain a large negative magnetic anisotropy necessary to improve their single-molecule-magnet (SMM) behavior has been studied. [source]

Synthesis, X-ray Single-Crystal Structure Determination, and Magnetic Properties of [Rb(benzo[18]crown-6)]+ Salts Containing Well-Ordered Fulleride Trianions C603,,

CHEMISTRY - A EUROPEAN JOURNAL, Issue 13 2009
Bele Boeddinghaus Dipl.-Chem.
Abstract Finally, a structure with well-resolved C603,ions and S=1/2 spin system: The two novel title compounds have clearly S=1/2 and not S=3/2 electronic states, as expected for the occupation of the triply degenerate LUMO of C60. These structures with well-ordered fullerene trianions show that the expected Jahn,Teller distortion is not observable in X-ray diffraction experiments. Crystals of the composition [Rb(benzo[18]crown-6)]3[,3 -C60](C7H8)(C3H7NO)4.5 (1) and [Rb(benzo[18]crown-6)]3[C60](C3H7NO)5.33(C4H8O)1.66 (2) were synthesized by reduction of C60 with elemental rubidium in a mixture of dimethylformamide/tetrahydrofuran in the presence of benzo[18]crown-6. X-ray single-crystal structure determinations reveal well-ordered C60 trianions in both compounds. In contrast to previously reported structures of compounds containing C603, ions the present structure refinements allow the description of the buckyballs with good resolution (R1/wR2 for I>2,(I) (all data) are 0.030/0.069 (0.051/0.071) and 0.042/0.101 (0.076/0.108) for 1 and 2, respectively). In 1 the C603, unit coordinates in an ,3 -fashion to one Rb atom, whose coordination sphere is completed by one benzo[18]crown-6 and one dimethylformamide molecule. In 2 no coordination of the alkali metal atom to the C60 trianion is observed. Magnetic measurements for 1 reveal a magnetic moment of 1.74,,B, as expected for an isolated S=1/2 spin system. The high-quality data of the present studies allowed a comparison of structural details of C603, ions with other C60n, units (n=0, 2, 3) and a discussion of the structural Jahn,Teller distortions. [source]

DommiMOE: An implementation of ligand field molecular mechanics in the molecular operating environment

JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2005
Robert J. Deeth
The ligand field molecular mechanics (LFMM) model, which incorporates the ligand field stabilization energy (LFSE) directly into the potential energy expression of molecular mechanics (MM), has been implemented in the "chemically aware" molecular operating environment (MOE) software package. The new program, christened DommiMOE, is derived from our original in-house code that has been linked to MOE via its applications programming interface and a number of other routines written in MOE's native scientific vector language (SVL). DommiMOE automates the assignment of atom types and their associated parameters and popular force fields available in MOE such as MMFF94, AMBER, and CHARMM can be easily extended to provide a transition metal simulation capability. Some of the unique features of the LFMM are illustrated using MMFF94 and some simple [MCl4]2, and [Ni(NH3)n]2+ species. These studies also demonstrate how density functional theory calculations, especially on experimentally inaccessible systems, provide important data for designing improved LFMM parameters. DommiMOE treats Jahn,Teller distortions automatically, and can compute the relative energies of different spin states for Ni(II) complexes using a single set of LFMM parameters. © 2004 Wiley Periodicals, Inc. J Comput Chem 26: 123,130, 2005 [source]

Raman phonons and Raman Jahn,Teller bands in perovskite-like manganites

JOURNAL OF RAMAN SPECTROSCOPY, Issue 10 2001
Milko N. Iliev
The perovskite-like manganites R1,xAxMnO3, where R is a trivalent rare earth or Y and A is a divalent alkaline earth element, are characterized by a strong interplay of magnetism, electric transport and crystallographic distortion. At doping levels 0.15 < x < 0.45 the materials exhibit colossal magnetoresistance near the concomitant ferromagnetic and insulator,metal transitions. At a fractional doping level, such as x = 0.5, the crystallographic and magnetic environment is strongly modified and charge ordering between Mn3+ and Mn4+ or phase separation takes place. In this work, the polarized Raman spectra of the orthorhombic and rhombohedral phases of parent RMnO3 compound were analyzed in close comparison with results of lattice dynamic calculations. We argue that the strong high-wavenumber bands between 400 and 700 cm,1, which dominate the Raman spectra of rhombohedral RMnO3 and magnetoresistive La1,xAxMnO3 are not proper Raman modes for the R3c or Pnma structures. Rather, the bands are of phonon density-of-states origin and correspond to oxygen phonon branches activated by the non-coherent Jahn,Teller distortions of the Mn3+O6 octahedra. The reduction of these bands upon doping of La1,xAxMnO3 and their disappearance in the ferromagnetic metallic phase support the model. The variation with temperature of the Raman spectra of La0.5Ca0.5MnO3 is also discussed. The results give a strong indication for charge and orbital ordering and formation of superstructure at low temperatures. Copyright © 2001 John Wiley & Sons, Ltd. [source]

Octahedral tilting in cation-ordered Jahn,Teller distorted perovskites , a group-theoretical analysis

ACTA CRYSTALLOGRAPHICA SECTION B, Issue 1 2010
Christopher J. Howard
Computer-based group-theoretical methods are used to enumerate structures arising in A2BB,X6 perovskites, with either rock-salt or checkerboard ordering of the B and B, cations, under the additional assumption that one of these two cations is Jahn,Teller active and thereby induces a distortion of the BX6 (or B,X6) octahedron. The requirement to match the pattern of Jahn,Teller distortions to the cation ordering implies that the corresponding irreducible representations should be associated with the same point in the Brillouin zone. Effects of BX6 (and B,X6) octahedral tilting are included in the usual way. Finally, an analysis is presented of more complex models of ordering and distortion as might lead to the doubling of the long axis of the common Pnma perovskite, observed in systems such as Pr1,,,xCaxMnO3 (x, 0.5). The structural hierarchies derived in this work should prove useful in interpreting experimental results. [source]

Symmetry rules and strain/order-parameter relationships for coupling between octahedral tilting and cooperative Jahn,Teller transitions in ABX3 perovskites.

ACTA CRYSTALLOGRAPHICA SECTION B, Issue 2 2009

Space groups, order-parameter and strain/order-parameter coupling relationships in ABX3 perovskite structures which combine cooperative Jahn,Teller distortions and octahedral tilting have been investigated from the perspective of group theory using the computer program ISOTROPY. Two common Jahn,Teller ordering schemes are associated with the irreducible representations and of the space group . A third, less-common ordering scheme is associated with . These combine with tilting instabilities associated with and to generate a predicted suite of Jahn,Teller structure types that includes many of the known structures of manganites, vanadates, Cu and Cr halides. Order-parameter coupling and possible phase transitions are described using Landau free-energy expansions, and general expressions for the relationships between symmetry-adapted spontaneous strains and particular order-parameter components are presented. These provide a general formal framework for determining structural evolution across multi-component order-parameter space and for characterizing the influence of tilting instabilities on Jahn,Teller instabilities or of Jahn,Teller ordering on octahedral tilting. [source]

Twinning and structure of Eu0.6Sr0.4MnO3

ACTA CRYSTALLOGRAPHICA SECTION C, Issue 1 2006
Nicola Rotiroti
The crystal structure of europium strontium manganese trioxide, Eu0.6Sr0.4MnO3, has been refined using a multiply twinned single crystal containing six twin components. The MnO6 octahedra show Jahn,Teller distortions with nearly fourfold symmetry, but the octahedral tilting scheme reduces the crystal symmetry to orthorhombic (space group Pbnm). The refinement of site occupancies and the analysis of difference Fourier maps show that the Eu3+ and Sr2+ cations occupy different crystallographic positions with eightfold and twelvefold coordination, respectively. [source]

Synthesis, X-ray Single-Crystal Structure Determination, and Magnetic Properties of [Rb(benzo[18]crown-6)]+ Salts Containing Well-Ordered Fulleride Trianions C603,,

Synthesis and Characterization of Mixed-Valent Manganese Phosphonate Cage Complexes

CHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2006
Maheswaran Shanmugam
Abstract The reaction of phenylphosphonic acid (PhPO3H2) with the mixed-valent basic oxo-centered manganese triangle [Mn3O(O2CCMe3)6(py)3] (1; where py=pyridine) in the presence of a suitable base gives four different manganese clusters depending on the identity of the base. The syntheses and structural characterization of [Mn18(,3 -O)8(PhPO3)14(O2CCMe3)12(py)6(H2O)2] (2), [Mn7(,3 -O)3(O3PPh)3(O2CCMe3)8(py)3] (3), [Mn9Na(,3 -O)4(,4 -O)2(O3PPh)2(O2CCMe3)12(H2O)2(H2O)0.67(Py)0.33] (4), and [Mn13(,3 -O)8(OMe)8(O3PPh)4(O2CCMe3)10] (5) are described. Complexes 4 and 5 are homovalent MnIII cages, while 2 and 3 contain divalent, trivalent, and/or tetravalent ions. All the manganese centers are valence-localized, the octahedral MnIII sites being recognizable by marked Jahn,Teller distortions. The magnetic properties of compounds 2,5 have been investigated in the polycrystalline state by magnetic susceptibility and high-field magnetization measurements, which reveal that spin ground states vary from 0,S,8. AC susceptibility measurements performed on 4 and 5, in the 1.6,10.0 K ranges show the presence of out of AC susceptibility signal (,M,,) for 4, and an effective energy barrier (Ueff) for the re-orientation of the magnetization is found to be 17 K, but for 5, the ,M,, maximum is found to be below 1.5 K. [source]