4d Elements Research Articles

Temperature and Light Induced Bistability in a Co3[Os(CN)6]2 6H2O Prussian Blue Analog

To expand the field of new cyanide materials of the 5d elements, we incorporated the [Os(CN)(6)](3-) anion into PB architectures in combination with the Co(II) cation. Herein, we report the first example of a photomagnetic PB analog containing Os(III) ions. In a similar vein as the prototypical CoFe PB analogs, this compound exhibits a wide variety of properties including Charge Transfer Induced Spin Transition (CTIST), Temperature Induced Excited Spin State Trapping (TIESST), and magnetic ordering.

Carbene–Transition Metal Complexes Formed by Double CH Bond Activation

The activation of a single sp(3) C-H bond of alkanes and their derivatives by electron-rich transition metal complexes has been a topic of interest since the landmark work by Bergman and Graham in 1982. Ten years later, it was shown that compounds of 5d elements, such as osmium and iridium, even enable a double alpha-C-H bond activation of alkane or cycloalkane derivatives containing an OR or NR(2) functional group, thus opening up a new route to obtain Fischer-type transition metal carbene complexes. Subsequent work focused in particular on the conversion of methyl alkyl and methyl aryl ethers into bound oxocarbenes and also of dimethyl amines to bound aminocarbenes. In the context of this work, it was recently shown that square-planar oxocarbene-iridium(I) complexes prepared in this way exhibit an unusual mode of reactivity: They react with CO(2), CS(2), COS, PhNCO, and PhNCS by an atom- or group-transfer metathesis, which has no precedent. Organic azides RN(3) and N(2)O behave similarly. Recent results confirm that this novel type of metathesis can be made catalytic, thus offering a novel possibility for C-H bond functionalization.

Crystal Structures of Ternary Ruthenium Ferrites SrM2±xRu4∓xO11 with M = Fe, Co and Magnetic and Transport Properties of Al‐doped Single Crystals

AbstractSingle crystals of SrM2±xRu4∓xO11 with M = Fe, Co with maximum width of 2 mm and a thickness around 0.05 mm were grown from a chloride flux. Sample compositions were determined from refinements of X‐ray diffraction data and microprobe analysis. The hexagonal crystal structure (space group P63/mmc, Z = 2) consists of basal‐plane layers of edge‐sharing octahedra (M,Ru)O6, which are connected along [001] by face‐sharing pairs of octahedra (M,Ru)2O9 and trigonal bipyramids MO5. A significant homogeneity range is generated by variable occupation of the octahedral sites by 3d and 4d elements. Aluminum is also found to substitute for transition elements in the octahedral sites. The title compounds are narrow‐gap semiconductors and soft ferromagnets with Curie temperatures that can substantially exceed room‐temperature, depending on composition. Aluminum doping significantly modifies the transport properties, but magnetic properties such as the Curie temperature, magnetization and anisotropy are less affected. Hall coefficient measurements reveal the predominant charge carriers are holes. The structural, electronic and magnetic properties suggest that these solid solutions are promising candidates for spin‐injection devices.

Revised relativistic basis sets for the 5d elements Hf–Hg

The relativistic double-zeta (dz) and triple-zeta (tz) basis sets for the 5d elements Hf-Hg have been revised for consistency with the recently optimized 4f basis sets. The new dz basis sets have 24 s functions instead of 22 s functions, and the new tz basis sets have 30 s functions instead of 29 s functions. New contraction patterns have been determined, including the 6p orbital.

Energy-Consistent Pseudopotentials for the 5d Elements—Benchmark Calculations for Oxides, Nitrides, and Pt2

The performance of new relativistic energy-consistent pseudopotentials for the 5d elements, adjusted to atomic valence spectra from multiconfiguration Dirac-Hartree-Fock calculations (J. Chem. Phys. 2009, 130, 164108.), is examined in coupled cluster and multireference configuration interaction benchmark calculations for the diatomics HfO, TaO, WO, ReN, OsN, IrN, and Pt(2), with basis sets of up to quintuple-zeta quality. The final accuracy reached for the oxides and nitrides, with corrections for pseudopotential errors (contributions from 4f shell correlation, for example), is 0.3 pm for bond lengths and 17 cm(-1) (1.5%) for harmonic vibrational frequencies. The spectroscopic constants of the ground state of Pt(2) can be reproduced with deviations of 3 pm for the bond length and 1 cm(-1) for the vibrational frequency, without any correction for pseudopotential errors.

The geometrical structure, electronic structure and magnetism of bimetallic Au n M2 (n=1, 2; M=Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd) clusters

The geometrical structure, stability, magnetism, and electronic structure of bimetallic clusters AuM2 and Au2M2, where M are 4d transition metal elements, are investigated systematically by using the first-principles method based on density functional theory. The calculation results show that there is a large amount of low-energy isomers with the very similar structure. AuM2 and Au2M2 clusters display dramatic magnetism. The magnetic moment of the 4d element is either enhanced or weakened with respect to the bulk value, which is largely dependent on the orbital exchange-splitting.

Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt

New relativistic energy-consistent pseudopotentials have been generated for the 5d transition metals Hf-Pt. The adjustment was done in numerical two-component multiconfiguration Hartree-Fock calculations, using atomic valence-energy spectra from four-component multiconfiguration Dirac-Hartree-Fock calculations as reference data. The resulting two-component pseudopotentials replace the [Kr]4d(10)4f(14) cores of the 5d transition metals and can easily be split into a scalar-relativistic and a spin-orbit part. They reproduce the all-electron reference energy data with deviations of approximately 0.01 eV for configurational averages and approximately 0.05 eV for individual relativistic states. Full series of correlation consistent basis sets from double to quintuple-zeta have also been developed in this work for use with the new pseudopotentials. In addition, all-electron triple-zeta quality correlation consistent basis sets are also reported in order to provide calibration for the pseudopotential treatment. The accuracy of both the pseudopotentials and basis sets are assessed in extensive coupled cluster benchmark calculations of atomic ionization potentials, electron affinities, and selected excitation energies of all the 5d metal atoms, including the effects of spin-orbit coupling.

Auxiliary Basis Sets for Density-Fitted MP2 Calculations: Correlation-Consistent Basis Sets for the 4d Elements.

Auxiliary basis sets for use in density fitting second-order Møller-Plesset perturbation theory and other correlated ab initio methods have been developed for the 4d transition metal elements Y-Tc and Rh-Pd (sets for Ru, Ag, and Cd are already available), to be used in conjunction with the correlation consistent basis sets with pseudopotentials cc-pVnZ-PP and aug-cc-pVnZ-PP. Correlation energy calculations for a test set of small- to medium-sized transition metal complexes encompassing a variety of oxidation states show that the error in using these auxiliary basis sets is around 3-4 orders of magnitude smaller than the error due to orbital basis set size. The effect of truncating the auxiliary basis sets to remove higher angular momentum functions is also considered.

Structural Characterization of PLD-grown Nanometer Size Ferromagnetic NiFeMo Films

AbstractThin films of 3 different thicknesses each of Ni83.2Fe3.3Mo13.5 and Ni83.1Fe6.0Mo10.9alloys have been grown using Pulsed Laser Deposition (PLD) technique. Our motivation is to investigate the magnetic properties of a few nm thick Ni alloys with mostly Mo (4d element) addition since the corresponding soft ferromagnetic bulk alloys have shown very small coercivity of ˜ 0.1 Oe. Detailed structural characterization has been undertaken before probing the magnetic properties. Arc melted alloy buttons after homogenization are used directly as targets for the deposition. Films were deposited on single crystal Sapphire (0001) substrates using excimer laser. The structural characterization has been done by X-ray diffraction (XRD), X-ray reflectivity (XRR), Energy dispersive x-ray spectroscopy (EDS), and Atomic force microscopy (AFM). The X-ray diffraction pattern shows that the films are highly textured and grown along [111] direction of the alloys. They have high lattice strain which makes the films highly resistive and the resistance decreases with increasing thickness. The EDS measurements, using Scanning electron microscope (SEM), indicate that the compositions of the films are almost the same as those of the targets. Thickness, roughness, and density gradients are estimated using XRR measurements. The thinner films have higher roughness compared to the thicker ones for both the compositions. The films have density gradient across their thickness. The bottommost low density layer has high roughness which is supposed to be the result of initial non uniform coverage of the substrate. The density of the middle layer, having the lowest roughness, is approximately near the bulk value and it increases with increasing film thickness. The change in density is not due to the variation of composition; instead it is due to the variation of void densities in the layers. The topmost layer, having the lowest density and the highest roughness, is interpreted as a porous layer which is also evident from the AFM images.

First-principles study of site occupancy of dilute 3d, 4d and 5d transition metal solutes in L1 0 TiAl

Using a statistical-mechanical Wagner–Schottky model parametrized by first-principles density-functional (DFT-GGA) calculations on 32-atom supercells, we predict the lattice site occupancy of 3d (Ti–Cu), 4d (Zr–Ag) and 5d (Hf–Au) transition-metal elements in L1 0 TiAl intermetallic compound as a function of both alloy composition and temperature. The effects of local atomic relaxations, anisotropic lattice distortions, as well as magnetism on point defect energetics are fully taken into account. Our calculations show that, at all alloy compositions and temperatures, Zr and Hf consistently show a preference for the Ti sublattice, while Co, Ru, Rh, Pd, Ag, Re, Os, Ir, Pt and Au consistently show a preference for the Al sublattice. In contrast, the site preference of V, Cr, Mn, Fe, Ni, Cu, Nb, Mo, Tc, Ta and W strongly depend on both alloy stoichiometry and temperature. Our calculated results compare favorably with the existing theoretical and experimental studies in the literature.

Assignment of pre‐edge peaks in K‐edge x‐ray absorption spectra of 3d transition metal compounds: electric dipole or quadrupole?

AbstractThe characteristics of pre‐edge peaks in K‐edge x‐ray absorption near edge structure (XANES) spectra of 3d transition metals were reviewed from viewpoints of the selection rule, coordination number, number of d‐electrons, and symmetry of the coordination sphere. The contribution of the electric dipole and quadrupole transition to the peaks was discussed on the basis of the group theory, polarized spectra, and theoretical calculations. The pre‐edge peak intensity for Td symmetry is larger than those for Oh symmetry for all 3d elements. The intense pre‐edge peak for tetrahedral species of 3d transition metals is not due to 1s–3d transition, but transition to the p component in d–p hybridized orbital. The mixing of metal 4p orbitals with the 3d orbitals depends strongly on the coordination symmetry, and the possibility is predictable by group theory. The transition of 1s electron to d orbitals is electric quadrupole component in any of the symmetries. The d–p hybridization does not occur with regular octahedral symmetry, and the weak pre‐edge peak consists of 1s–3d electric quadrupole transition. The pre‐edge peak intensity for a compound with a tetrahedral center changes as a function of the number of 3d electrons regardless of the kind of element; it is maximized at d0 and gradually decreases to zero at d10. The features of pre‐edge peaks in K‐edge XANES spectra for 4d elements and the L1‐edge for 5d elements are analogous with those for 3d elements, but the pre‐edge peak is broadened due to the wide natural width of the core level. Copyright © 2008 John Wiley & Sons, Ltd.

Crystal chemical simulation of superconductors on the basis of oxide and intermetalliclayers

Simulation of ‘hybrid’ superconductors of 3d, 4d and 5d transition elements consisting oftwo different superconducting fragments located between positively charged ionsplanes—B′O2 oxideplanes and B2C2 intermetallic layers—has been performed on the basis of the structure ofSr2Mn3As2O2 (A2(B2C2)(B′O2)). The oxide planesare similar to those of CuO2 in high-temperature superconducting cuprates while the intermetallic layers are similar to those ofNi2B2 in low-temperature superconducting borocarbidesRNi2B2C and Fe2As2 layers in high-temperature superconducting oxypnictidesRFeAsO1−xFx.

On the Mechanisms of Degenerate Ligand Exchange in [M(CH3)]+/CH4 Couples (M=Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) as Explored by Mass Spectrometric and Computational Studies: Oxidative Addition/Reductive Elimination versus σ‐Complex‐Assisted Metathesis

The degenerate ligand exchange in [M(CH(3))](+)/CH(4) couples occurs in the gas phase at room temperature for M=Ni, Ru, Rh, Pd, and Pt, whereas the complexes containing Fe and Co are unreactive. Details of hydrogen-atom scrambling versus direct ligand switch have been uncovered by labeling experiments with CD(4) and (13)CH(4), respectively. The reactivity scale ranges from unreactive (M=Fe, Co) or inefficient (M=Ni, Pd) to moderately (M=Ru) and rather reactive (M=Rh, Pt). Quite extensive, but not complete, H/D exchange between the hydrogen atoms of the incoming and outgoing methyl groups is observed for M=Pt, whereas for M=Ni and Pd a predominantly direct ligand switch prevails. DFT calculations performed at the B3LYP level of theory account well for the thermal nonreactivity of the Fe and Co couples. For [Ni[CH(3))](+)/CH(4), a sigma-complex-assisted metathesis (sigma-CAM) is operative such that, in a two-state reactivity (TSR) scenario, two spin flips between the (3)A ground and (1)A excited states take place at the entrance and exit channels of the encounter complexes. For M=Ru and Rh, only oxidative addition/reductive elimination (OA/RE) is favored energetically, and the reaction is confined to the electronic ground states (3)A and (2)A. In contrast, for the [Pd(CH(3))](+)/CH(4) system, on the (1)A ground-state potential-energy surface both the OA/RE and sigma-CAM variants are energetically comparable, and the small reaction efficiency for the ligand switch is reflected in transition states located energetically close to the reactants. For the [M(CH(3))](+)/CH(4) complexes of the 5d elements, the sigma-CAM mechanism does not play a role. For M=Pt, the energetically most favored path proceeds in a spin-conserving manner on the (1)A potential-energy surface, which accounts for the extensive single and double hydrogen-atom exchange preceding ligand exchange. Although for M=Os and Ir the [M(CH(3))](+) complexes could not be generated experimentally, computational studies predict that both systems may undergo thermal reaction with CH(4), and an OA/RE mechanism will commence on the respective high-spin ground states; however, the bond-activation and ligand-exchange steps will occur on the excited low-spin surfaces in a TSR scenario.

Structural, magnetic, and transport properties of a novel class of ferromagnetic semiconductors: SrM2±xRu4±xO11 (M=Fe,Co)

A major obstacle to the implementation of spin-polarized semiconductor devices is the current absence of suitable room-temperature, soft ferromagnetic semiconductors (FSs). Dilute magnetic semiconductors are under intense study for applications in spintronics. However, the weak solubility of randomly placed magnetic ions in the semiconductor host makes these materials unsuitable for devices. It is, therefore, crucial to develop a room-temperature FS based on a periodic array of magnetic ions. We have found that ternary ruthenium ferrites exhibit long-range ferromagnetic order well above room temperature, accompanied by narrow-gap semiconducting properties that include a large anomalous Hall conductance, low resistivity, and high carrier concentration. The physical properties can be tuned by simple chemical substitution of two elements, Fe and Co, or by varying the relative concentration of 3d and 4d elements within a homogeneity range that we have established. These promising properties—manifest within a single structural family—provide a fertile ground for fundamental studies and open up a host of potential device applications.

Energy-consistent relativistic pseudopotentials for the 4d elements: Atomic and molecular applications

Recently reported energy-consistent relativistic pseudopotentials have been used with series of matching correlation consistent basis sets in benchmark calculations of various atomic and molecular properties. The basis set convergence of the 4d metal electron affinities and 5s2-->5s0 excitation energies are reported at the CCSD(T) level of theory, and the effects of valence and 4s4p correlation are investigated. In addition the impact of correlating the low-lying 3d electrons was also studied in all-electron Douglas-Kroll-Hess (DKH) calculations, which also included the ionization potentials and 5s2-->5s1 excitation energies. For all four atomic properties, higher order coupled cluster calculations through CCSDTQ are reported. The final calculated values are generally all within 1 kcal/mol of experiment. A notable exception is the ionization potential of Tc, the currently accepted experimental value of which is suggested to be too high by about 3 kcal/mol. Molecular calculations are also reported for the low-lying electronic states of ZrO and RuF, as well as the ground electronic state of Pd2. The effects of spin-orbit coupling are investigated for these cases in pseudopotential calculations. Wherever possible, the pseudopotential results have been calibrated against DKH calculations with correlation consistent basis sets of triple-zeta quality. In all cases the calculated data for these species are in very good agreement with experiment. In particular, the correct electronic ground state for the RuF molecule (4Phi92) was obtained, which was made possible by utilizing systematic sequences of correlation consistent basis sets.

Olefin Substitution in (silox)3M(olefin) (silox = tBu3SiO; M = Nb, Ta): The Role of Density of States in Second vs Third Row Transition Metal Reactivity

The substitution chemistry of olefin complexes (silox)3M(ole) (silox = (t)Bu3SiO; M = Nb (1-ole), Ta (2-ole); ole = C2H4 (as 13C2H4 or C2D4), C2H3Me, C2H3Et, cis-2-C4H8, iso-C4H8, C2H3Ph, cC5H8, cC6H10, cC7H10 (norbornene)) was investigated. For 1-ole, substitution was dissociative (deltaG(double dagger)(diss)), and in combination with calculated olefin binding free energies (deltaG(o)(bind)), activation free energies for olefin association (deltaG(double dagger)(assoc)) to (silox)3Nb (1) were estimated. For 2-ole, substitution was not observed prior to rearrangement to alkylidenes. Instead, activation free energies for olefin association to (silox)3Ta (2) were measured, and when combined with deltaG(o)(bind) (calcd), estimates of olefin dissociation rates from 2-ole were obtained. Despite stronger binding energies for 1-ole vs 2-ole, the dissociation of olefins from 1-ole is much faster than that from 2-ole. The association of olefins to 1 is also much faster than that to 2. Linear free energy relationships (with respect to deltaG(o)(bind)) characterize olefin dissociation from 1-ole, but not olefin dissociation from 2-ole, and olefin association to 2, but not olefin association to 1. Calculated transition states for olefin dissociation from (HO)3M(C2H4) (M = Nb, 1'-C2H4; Ta, 2'-C2H4) are asymmetric and have orbitals consistent with either singlet or triplet states. The rearrangement of (silox)3Nb(trans-Vy,Ph-cPr) (1-VyPhcPr) to (silox)3Nb=CHCH=CHCH2CH2Ph (3) is consistent with a diradical intermediate akin to the transition state for substitution. The disparity between Nb and Ta in olefin substitution chemistry is rationalized on the basis of a greater density of states (DOS) for the products (i.e., (silox)3M + ole) where M = Nb, leading to intersystem crossing events that facilitate dissociation. At the crux of the DOS difference is the greater 5dz2/6s mixing for Ta vs the 4dz2/5s mixing of Nb. This rationalization is generalized to explain the nominally swifter reactivities of 4d vs 5d elements.

An optical excitation study of Ru‐, Rh‐, Re‐ and Os‐doped Bi12SiO20 crystals

AbstractWe studied the influence of doping with 4d and 5d elements on the optical and photo‐induced properties of Bi12SiO20 (BSO) crystals. Doping with Ru, Rh and Re does not significantly influence BSO absorption spectra as well as photo‐induced absorption and photocurrent in BSO. On the other hand, doping with Os with concentration of 0.0004 mass% increases by more than an order of magnitude the illumination response time, the strength of the photochromic effect and photocurrent, all this being accompanied by only a slight change of the absorption coefficient as compared to undoped BSO. The observed effects are explained in the framework of the Rose model assuming that doping with Os creates deep levels in the gap that act as recombination centers with a very little cross‐section of electron capture. We also studied the kinetic curves of photocurrent increase and decrease in BSO:Os which enabled us to determine the magnitude of the cross‐section of a photon capture at an impurity center. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Chemical Bonding in Metallic Rutile-type Oxides TO2 (T = Ru, Rh, Pd, Pt)

Abstract Synthesis routes to rutile-type oxides with 4d and 5d transition elements are summarized. Trends in electronic structure have been established through an analysis in the framework of density functional theory presenting the band structure, the density of states and the properties of chemical bonding. The metal-oxygen bond is found to play the major role in bonding of the system in the valence band. Throughout the series 4d → 5d (RuO2, RhO2, PdO2 and PtO2) the crystal field analysis of the band structure shows a lowering of eg towards t2g manifolds and a broadening of the overall density of states. In the vicinity of the Fermi level the role of the antibonding metal-oxygen character is investigated in the context of instability towards possible magnetic polarization, especially for RuO2.

Energy Decomposition Analysis of Metal—Metal Bonding in [M2X8]2‐ (X: Cl, Br) Complexes of 5f (U, Np, Pu), 5d (W, Re, Os), and 4d (Mo, Tc, Ru) Elements.

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Site preference of transition-metal elements in B2 NiAl: A comprehensive study

First-principles supercell calculations based on density functional theory were performed to study the T = 0 K site preference of 3d (Ti–Cu), 4d (Zr–Ag) and 5d (Hf–Au) transition-metal elements in B2 NiAl. By adopting a statistical-mechanical Wagner–Schottky model within the canonical ensemble, the effects of finite temperature on site preference were further considered. The calculations showed that, at all alloy compositions and temperatures, Co, Tc, Ru, Rh, Re, Os, Ir and Pt have a consistent preference for the Ni sublattice, while Ti, Zr, Nb, Hf and Ta have a consistent preference for the Al sublattice. In contrast, the site preference of V, Cr, Mn, Fe, Cu, Mo, Pd, Ag, W and Au was found to depend on both composition and temperature. The present calculated results compare favorably with existing theoretical and experimental studies in the literature.