Correlation energy in a transition metal

Correlation energies of the nondegenerate and the degenerate Hubbard models are calculated with second order perturbation theory and with a variational local ansatz. By comparing these results, we discover an overestimate of the correlation energy in the perturbation treatment. The overestimate is due to the independent treatment of electron correlations in different orbital states. We also demonstrate the qualitative difference in electron correlation between the two models.     

An energy band calculation of linear chain transition metal complexes

The energy band structure of a class of linear chain compounds is investigated using a modification of the Green's Function Method. A discussion of the implications of the band structure to the properties of compounds in this class is presented.     

Particular features of manifestation of energy migration toward impurity in nanoparticles of metal complexes

We measure the fluorescence quantum yields (q _fl) of complexes of Al, Sc, Y, In, Lu, and Gd with dibenzoylmethane in aqueous and isopropanol solutions at different concentration ratios of ions and dike-tone. We reveal that, for the examined solutions, qfl of complexes varies more than by two orders of magnitude under the influence of the heavy atom. It is found that a considerable decrease in q _fl and τ_fl of ligands of complexes of listed ions caused by the influence of heavy atoms weakly affects the intensity of sensitized fluorescence of Nile red and rhodamine 6G molecules introduced into nanoparticles from these complexes in aqueous solutions. The revealed result is explained by the comparability of the singlet exciton free path length and the dimension of nanoparticles under study. We show that a lower fluorescence intensity of heavy metal complexes makes it possible to decrease its contribution in the range of the cofluorescence maximum of rhodamine 6G and to monitor the occurrence of the dye in the aqueous solution down to the concentration of 0.05 nM. We show that, in nanoparticles from Eu complexes, further fluorescence quenching of dibenzoylmethane is observed, as well as the appearance of cofluorescence of rhodamine 6G, the intensity of which is comparable with its intensity in nanoparticles of other complexes. The appearance of this cofluorescence cannot be explained by the existence of S-S energy migration.     

Photoluminescence of transition metal complexes in silicon

Results of luminescence studies on silicon doped with the 3d transition metals are reviewed. Spectra are observed after V, Cr, Mn, Fe, and Cu diffusion. We discuss the problems of center identifications, using the example of the CrB-pair luminescence. Level schemes for the optical transitions are discussed and correlated with electrical level positions of TM defects. Luminescent centers can be divided into two classes: CrB,CrGa, and Mn₄ are effective recombination centers with low quantum efficiencies, whereas Fe and Cu associated spectra show characteristics of exciton decay at isoelectronic centers, e.g. show a high quantum efficiency. The phonon structure of the spectra is discussed, and it is shown that the local mode energies of the centers follow a systematic trend.     

Probing depth of the low energy cascade electrons from a transition metal

A surface probing depth of only 2 layers for low energy cascade electrons excited with a 3.2 keV primary electron beam is clearly demonstrated by model experiments with non-magnetic overlayers of Ta on magnetic substrates of Fe/Ni₈₀Fe₂₀. This result establishes a short probing depth of low energy electrons in transition metals generalizing the previously observed short magnetic probing depth for spin-polarized electrons in ferromagnets. The short probing depth sheds new light on a number of spectroscopic observations on ferromagnetic transition metals, and has important implications concerning surface magnetic properties and scattering processes of hot electrons in transition metals.     

Modelling the energy gap in transition metal/aluminium bilayers

We present an application of the generalised proximity effect theory. The theory has been used to determine the energy gap (Δ_g) in proximised transition metal/aluminium bilayer structures such as Nb/Al, Ta/Al, V/Al and Mo/Al. These bilayers have different film thicknesses ranging from 5 to 260 nm. For the cases of Nb/Al, Ta/Al and V/Al bilayers, the interface parameters γ and γ_BN (here we define γ as the ratio of the products of normal state resistivity and coherence length in each film of the bilayer while γ_BN is the ratio of the boundary resistance between films 1 and 2 to the product of the resistivity and coherence length in the second film), which were used as input parameters to the model, were inferred experimentally from an existing bilayer of each kind and then suitably modified for different film thicknesses. This experimental assessment is therefore based on a comparison of measurements of the critical temperature and the energy gap at 300 mK with the predictions from the model for various values of γ, γ_BN. The energy gap of the bilayer was experimentally determined by using symmetrical superconducting tunnel junctions (STJs) of the form S–Al–AlO_x–Al–S, where each electrode corresponds to a proximised bilayer. However for the case of Mo/Al bilayers the interface parameters were determined theoretically since currently no STJ data for this configuration are available. The results for the Nb/Al, Ta/Al and V/Al bilayers have also then been compared to experimentally determined energy gaps found for a series of STJs with different film thicknesses. The correspondence between experiment and theory is very good.     

Exciton binding energy in a double quantum well: effect of the barrier shift

We have calculated the exciton binding energy in an Al _xGa_1 − x As  / GaAs double quantum well by a variational envelope function procedure using a simple two-band model. The influence of the shift of the AlAs separating barrier, introducing an asymmetry into the system, on the value of the exciton binding energy has been analysed. It has been observed that this shift induces significant changes of the exciton binding energy—even several meVs in the case of very thin barriers.     

Valence bond analysis of the bonding in transition metal compounds: the RuNO group in nitrosyl complexes

The ab initio and semi-empirical configuration interaction wave functions of ruthenium complexes [RuL₅(XY) ^q (L &; = NH₃, Cl^?, CN^?, XY &;= N₂, CO) are presented in the form of linear combinations of the valence bond (VB) structures, each structure being referred to some covalent or ionic model of the bonding in the M-XY group. The results of this VB analysis showed that [RuL₅(NO)] ^q complexes can be described as compounds of Ru(III) and neutral NO⁰ with a covalent π-bond in addition to the usual coordination bond.     

Electron-longitudinal-phonon coupling in a transition metal: Ta

Recent tunneling studies of tantalum using a proximity technique reveal stronger coupling to the longitudinal modes relative to the transverse modes than observed previously for any transition metal. This result has implications for modeling the electron-phonon coupling mechanism and for future tunneling investigations. We obtain parameter values for Ta of $\text{λ = 0.73, μ}{}_{\mathrm{ph}}{}^1\text{= 0.10}$,in agreement with optimized conventional results.     

Role of kinematic factors in the manifestation of CO and CC vibrations in β-diketonate metal complexes

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 5, pp. 736–739, May, 1991.     

The nature of the vectorial photoelectric effect in the threshold energy region

Summary An immediate correlation has been proved to exist between the vectorial photoelectric effect and electronic surface structure modified due to adsorption. Experimental studies were performed for Cs overlayers on W(110) and Si(111) faces using visible exciting photons with energies below those of both bulk and surface plasmons. Considerable (more than 20 fold) growth of the effect was observed forp-polarized light in the vicinity of threshold as the light frequency approached the position of the maximum of local density in the surface-state band. A special case of the vectorial photoelectric effect forp-polarized light has been found in the absence of bulk photoemission excited bys-polarized light. Our results prove that the anomalous vectorial photoelectric effect is caused by the normal electric vector component of thep-polarized light under appropriate conditions for the particular photoemission enhancement on the surface. The effect can be related to optical absorption by the surface-state band and to subsequent electron emission into the vacuum, the normal electric vector component of thep-polarized light being essential for both processes.     

Photorefractive effect of a novel conjugate polymer containing transition metal complex

The photorefractive effect (PR) of a novels σ-π alternating polymer having 2,2'-bipyridyl in the polymer backbone and their ruthenium complexes has been investigated. The ruthenium complex was used as the charge generator, the σ-π alternating polymer backbone as the charge transporting channel and second-order nonlinear (NLO) optical chromophore. The photorefractive properties were demonstrated by two-beam coupling (2BC), degenerated four-wave mixing (DFWM) and field-induced orientation birefringence at wavelength of 532 nm. This polymer shows a enhanced photorefractive effect due to the efficient photoinduced metal-to-ligand charge transfer (MLCT) inside the ruthenium complex. A net optical gain of about 22 cm^-1 and the diffraction efficiency about 10% were obtained at the external electric field of 30 V/μm. Received 21 December 1999 and Received in final form 7 July 2001     

Local environment effect on the superconductivity of transition metal alloys

We show that for superconductor vanadium based alloys in the split-band limit the calculated critical temperature is in agreement with experimental data if one assumes that these alloys have a short-range order favouring clusters of pure vanadium.     

On the nature of the magnetic transition in a Mott insulator

Using a combination of exact enumeration and the dynamical mean-field theory (DMFT) we study the drastic change of the spectral properties, obtained in the half-filled two-dimensional Hubbard model at a transition from an antiferromagnetic to a paramagnetic Mott insulator, and compare it with the results obtained using the quantum Monte Carlo method. The coherent hole (electron) quasiparticle spin-polaron subbands are gradually smeared out when the AF order disappears, either for increasing Coulomb repulsion U at fixed temperature T, or for increasing T at fixed U. Within the DMFT we present numerical evidence (a continuous disappearence of the order parameter) suggesting that the above magnetic transition is second order both in two and in three dimensions.Received: 20 November 2004, Published online: 9 April 2004PACS: 71.30. + h Metal-insulator transitions and other electronic transitions - 71.10.Fd Lattice fermion models (Hubbard model, etc.) - 79.60.-i Photoemission and photoelectron spectraThis work is dedicated to Professor Ole Krogh Andersen on the occasion of his 60th birthday.     

Acceleration of particles by black holes as a result of deceleration: Ultimate manifestation of kinematic nature of BSW effect

The recently discovered so-called BSW effect consists in the unbound growth of the energy _Ec.m.$E_{\mathit{c}.\mathit{m}.}$ in the center of mass frame of two colliding particles near the black hole horizon. We consider a new type of the corresponding scenario when one of two particles (“critical”) remains at rest near the horizon of the charged near-extremal black hole due to balance between the attractive and repulsion forces. The other one hits it with a speed close to that of light. This scenario shows in a most pronounced way the kinematic nature of the BSW effect. In the extremal limit, one would gain formally infinite _Ec.m.$E_{\mathit{c}.\mathit{m}.}$ but this does not happen since it would have require the critical massive particle to remain at rest on the null horizon surface that is impossible. We also discuss the BSW effect in the metric of the extremal Reissner–Nordström black hole when the critical particle remains at rest near the horizon.     

A Q-band pulsed ENDOR spectrometer for the study of transition metal ion complexes in solids

We describe the design of a pulsed electron nuclear double resonance (ENDOR) spectrometer operating at Q-band frequencies (35 GHz) for studies of transition metal ion complexes in the temperature range between 4.2 and 297 K. Specific features of the spectrometer are a microwave IMPATT generator, a homebuilt cavity, and a commercial Bruker magnet. Standard Davies and Mims ENDOR sequences have been implemented. The performance of the spectrometer is demonstrated for a broad radio frequency range by¹H,¹⁴N,³¹P,¹³³Cs, and²⁰⁷Pb pulsed ENDOR experiments of Cu²⁺, Cr⁵⁺, and V⁴⁺ transition metal ion complexes in both single crystals and disordered materials.     

Lithium intercalation complexes of layered transition metal dichalcogenides: An NMR survey of physical properties

NMR studies of lithium intercalation complexes of layered disulfides and diselenides of Group IVb and Vb transition metals establish that the inclusion of a guest lithium atom between the host dichalcogenide layers is accompanied by the donation of approximately one electron to the host. Measurements of the electrostatic and magnetic interactions between the lithium atom and the host and the rate of lithium atom motion are discussed.     

Investigation of the doped transition metal promotion effect on CO2 chemisorption on Ni (1 1 1)

The chemisorption of CO₂ on the pure Ni (1 1 1) and doped Ni (1 1 1) by transition metal (Co, Rh, Cr, Ce, La) were investigated by using the generalized gradient approximation (GGA) and the Perdew–Burke–Emzerhof (PBE) functional. The optimized structure of doped metal surface showed that Rh, Cr, Ce, La atoms upward shift from the surface of Ni (1 1 1) plane, while the atom radius of Co is the minimum offset which lead to the height is ?0.03 Å. The ability of CO₂ chemisorption follows the order of La/Ni (1 1 1) > Ce/Ni (1 1 1) > Cr/Ni (1 1 1) > Co/Ni (1 1 1) > pure Ni (1 1 1). It is exothermic when CO₂ chemisorbed on Cr/Ni (1 1 1) Ce/Ni (1 1 1) and La/Ni (1 1 1), while it is endothermic on the Co/Ni (1 1 1) and pure Ni (1 1 1). CO₂ molecular chemisorbed on all the metal surfaces are negatively charged, result from the electron transfer between the metal surfaces and the CO₂ molecular. The transition metals La, Ce and Cr can promote the transformation of electron and make the CO bonds longer than the pure Ni (1 1 1). We also analyzed the dissociation of CO₂ on the Ni-based surface and found that the La/Ni (1 1 1) surface is the preference surface for the dissociation of CO₂, which improved the ability to hinder carbon deposition.     

On the nature of a new phase transition in α-MnS

Magnetic-susceptibility and X-ray-diffraction data of polycrystalline and oriented single crystal α-MnS reveal a new phase transition at T_tr = 131 K below the Néel temperature T_N = 148 K. The phase transition is characterized by an abrupt inversion of the rhombohedral distortion of the f.c.c. lattice along [111]. At T_tr there is a discontinuous change in the susceptibility of single crystals.