Rydberg Spectroscopy of Transition—Metal Sandwich Compounds

ChemInform ◽  
2007 ◽  
Vol 38 (6) ◽  
Author(s):  
Sergey Yu. Ketkov
2020 ◽  
Vol 49 (3) ◽  
pp. 569-577 ◽  
Author(s):  
Sergey Ketkov

High-resolution threshold ionization spectroscopy reveals new aspects of substituent effects in transition-metal sandwich complexes.


1984 ◽  
Vol 39 (3) ◽  
pp. 223-246
Author(s):  
Michael C. Böhm

AbstractThe band structures of 11 one-dimensional (ID) poly-decker sandwich compounds with dif­ferent transition metal centers M (M = Mn, Fe, Co, Ni, Cu, Zn) and a variety of fivemembered π ligands L from the cyclopentadienyl moiety (C5H5) to the pure boron ring B5H5 have been studied by means of a semiempirical crystal orbital procedure based on the INDO approxima­tion in order to allow a priori predictions on possible semiconducting or conducting low-dimen­sional materials composed by ML fragments. To determine the (numerically) different self­energy corrections (i.e. long-range and short-range “correlations”) in the transition metal 3d spines and the ligand backbones approximate quasi-particle shifts have been employed for the correction of the Hartree-Fock (HF) band energies. The band structure properties (e.g., dispersion curves, density of states distributions, effective mass parameters, propagation times of charge carriers) are discussed in the light of the semiempirical tight-binding approach. It is shown that the forbidden band gaps are reduced with an increasing number of B atoms in the π ligands. The gap in the Mn(C5H5) stack amounts to 8.27 eV, while overlapping dispersion curves are predicted in the Zn(B5H5) derivative. This model polymer is the only intrinsic conductor in the series of the studied ID metallocenes; all other compounds require injected charge carriers (electrons or holes) in order to achieve partially filled bands. Injected holes in the Mn or Fe backbones lead to ID materials with conducting 3d spines; the charge transfer in this regime is best described as some type of hopping motion. The remaining poly-decker strands belong to the class of organic metals (injected carriers) with conductive pathways that are formed by diffuse ligand states leading to transfer processes that can be rationalized in terms of a band picture. The rotational profiles and the magnitudes of intracell and intercell interactions are also studied. The band structure properties (band gaps, characters of the valence and conduction bands) depend critically on the mutual orientations between neighbouring unit cells in the case of ligands with low spatial symmetries. General rules and strategies for synthetic approaches to organometallic ID materials containing 3d centers with small or vanishing band gaps are formulated.


2009 ◽  
Vol 429 (1) ◽  
pp. 258-263 ◽  
Author(s):  
T. N. Gribanova ◽  
R. M. Minyaev ◽  
V. I. Minkin

Author(s):  
R. Ai ◽  
H.-J. Fan ◽  
L. D. Marks

It has been known for a long time that electron irradiation induces damage in maximal valence transition metal oxides such as TiO2, V2O5, and WO3, of which transition metal ions have an empty d-shell. This type of damage is excited by electronic transition and can be explained by the Knoteck-Feibelman mechanism (K-F mechanism). Although the K-F mechanism predicts that no damage should occur in transition metal oxides of which the transition metal ions have a partially filled d-shell, namely submaximal valence transition metal oxides, our recent study on ReO3 shows that submaximal valence transition metal oxides undergo damage during electron irradiation.ReO3 has a nearly cubic structure and contains a single unit in its cell: a = 3.73 Å, and α = 89°34'. TEM specimens were prepared by depositing dry powders onto a holey carbon film supported on a copper grid. Specimens were examined in Hitachi H-9000 and UHV H-9000 electron microscopes both operated at 300 keV accelerating voltage. The electron beam flux was maintained at about 10 A/cm2 during the observation.


Author(s):  
Michel Fialin ◽  
Guy Rémond

Oxygen-bearing minerals are generally strong insulators (e.g. silicates), or if not (e.g. transition metal oxides), they are included within a rock matrix which electrically isolates them from the sample holder contacts. In this respect, a thin carbon layer (150 Å in our laboratory) is evaporated on the sections in order to restore the conductivity. For silicates, overestimated oxygen concentrations are usually noted when transition metal oxides are used as standards. These trends corroborate the results of Bastin and Heijligers on MgO, Al2O3 and SiO2. According to our experiments, these errors are independent of the accelerating voltage used (fig.l).Owing to the low density of preexisting defects within the Al2O3 single-crystal, no significant charge buildup occurs under irradiation at low accelerating voltage (< 10keV). As a consequence, neither beam instabilities, due to electrical discharges within the excited volume, nor losses of energy for beam electrons before striking the sample, due to the presence of the electrostatic charge-induced potential, are noted : measurements from both coated and uncoated samples give comparable results which demonstrates that the carbon coating is not the cause of the observed errors.


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