Intercalation of tris-(2,2′-bipyridyl) ruthenium (II) in α- and γ-zirconium phosphate: synthesis, thermal behaviour and X-ray characterization

Intercalation compounds such as the ruthenium trisbipyridyl complex in inorganic layered ion-exchangers (α- and γ-zirconium phosphate) have been synthesized using the batch method. There is no loss of bipyridyl ligand from the metal ion during the exchange of the ruthenium trisbipyridyl complex in these host matrices. The materials obtained are thermally stable up to ~330 °C (γ-phase) or ~380 °C (α-phase). The complex decomposition occurs in one or more steps and at ~600 °C the complex decomposition is complete. The X-ray patterns of ruthenium materials show a new phase with an increase in the interlayer distance with respect to the initial phase. Microanalysis measurements confirm the fact that the ruthenium complex is not modified when exchanged and the complex decomposition depends on its position in the host matrices.     

Nuclear quantum effects in calculated NMR shieldings of benzene; a Feynman path integral study

The Feynman path integral Monte Carlo approach has been coupled to the gauge including atomic orbital formalism in order to analyse the absolute magnetic shieldings of the benzene nuclei under the conditions of thermal equilibrium. The Hamiltonian employed in the derivation of ensemble averaged NMR quantities is of the Hartree-Fock type. The basis set used is of 6–31G quality. The spatial delocalization of the atoms leads to a deshielding of both types of benzene nuclei relative to the shieldings experienced at the minimum of the potential energy surface. This deshielding has to be traced back to bond length elongations in thermal equilibrium. The influence of the nuclear fluctuations on the NMR parameters of benzene is quantum driven up to temperatures of 400 K; classical fluctuations are of minor importance in this low-temperature window.     

Nitrogen binding to the FeMo-cofactor of nitrogenase

Density functional calculations are presented to unravel the first steps of nitrogen fixation of nitrogenase. The individual steps leading from the resting state to nitrogen binding at the FeMo-cofactor with a central nitrogen ligand are characterized. The calculations indicate that the Fe-Mo cage opens as dinitrogen binds to the cluster. In the resting state, the central cage is overall neutral. Electrons and protons are transferred in an alternating manner. Upon dinitrogen binding, one protonated sulfur bridge is broken. An axial and a bridged binding mode of dinitrogen have been identified. Adsorption at the Mo site has been investigated but appears to be less favorable than binding at Fe sites.     

Application of standard DFT theory for nonbonded interactions in soft matter: prototype study of poly-para-phenylene

We present a detailed analysis of the application of density functional theory (DFT) methods to the study of structural properties of molecular and supramolecular systems, using as a paradigmatic example three para-phenylene-based systems: isolated biphenyl, single chain poly-para-phenylene, and crystalline biphenyl. We use different functionals for the exchange correlation potential, the local density (LDA), and generalized gradient approximations (GGA), and also different basis sets expansions, localized, plane waves (PW), and mixed (localized plus PW), within the reciprocal space formulation for the hamiltonian. We find that regardless of the choice of basis functions, the GGA calculations yield larger interring distances and torsion angles than LDA. For the same XC approximation, the agreement between calculations with different basis functions lies within 1% (LDA) or 0.5% (GGA) for distances, and while PW and mixed basis calculations agree within 1 degrees for torsion angles, the localized basis results show larger angles by approximately 8 degrees and a nonmonotonic dependence on basis size, with differences within 6 degrees. The most prominent features, namely the torsion between rings for isolated molecule and infinite chain, and planarity for the molecule in crystalline environment, are well reproduced by all DFT calculations.     

Isomer shifts in Zr2Fe and Zr3Fe

The⁵⁷Fe isomer shifts in the crystalline compounds Zr₂Fe and Zr₃Fe are calculated. We use the standard first-principles linear-muffin-tin-orbital formalism in the atomic sphere approximation (LMTO-ASA) to obtain the electronic structure of the compounds. The electronic structure of pure Fe was also calculated with the same formalism, where the local spin density approximation for the exchange correlation term is used. We found that the calculated isomer shift values are in good agreement with the experimental values for Zr₂Fe and Zr₃Fe found in the literature.     

First application of the real space linear muffin-tin orbital atomic sphere approximation method for calculating Fermi contact hyperfine fields

In this work we apply the recently developed first-principles real space linear muffin-tin orbital atomic sphere approximation (RS-LMTO-ASA) scheme to calculate the hyperfine field for 3d impurities (V, Cr, Mn andFe) in Cu. We obtain the Fermi contact term at the impurities andat four shells of host atoms around the impurities. We compare our results with theoretical values obtained using the KKR-Green-function method andwith NMR measurements. The overall agreement is excellent, confirming the reliability of the RS-LMTO-ASA approach as means of obtaining information on hyperfine fields.     

Synthesis and characterization of sol-gel zirconium phosphate with template surfactants by different methods

Long chain trimethylammonium salts can be successfully used as guest molecules to produce mesoporous layered materials when intercalated in sol-gel zirconium phosphate, an inorganic ion-exchanger. The obtained materials are very similar independently of the chain length and the synthesis method batch (B) or direct intercalation (DI). They show a good thermal stability, and a very high interlayer distance if compared with their precursor. By the thermal characterization it can be observed that the surfactant is lost in two or three steps depending on its position in the host. The layered structure with the expanded interlayer distance is maintained up to 300°C. From the IR spectra the different surfactant release models for (B) and (DI) are confirmed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Distribution of electric field gradient at the nucleus for a cluster of amorphous Zr

In this work we apply the recently developed real space scheme based on the recursion method and the LMTO-ASA formatism to investigate the dominant p valence contribution to the distribution of electric field gradient at the nucleus (EFG) in amorphons metals. The Zr eluster was obtained by random packing of spheres with periodic boundary conditions. We find that the distribution of EFG is over positive and negative values and has a gap around zero.