Coordination of Cu(II) and Ni(II) in polymers imprinted so as to optimize amine chelate formation

Molecular imprinting has become an established technique. However, little was done on direct investigation of the sorbents produced. In the present work, en ESR method was used for the investigation of the complex formation processes within the sorbents imprinted with copper(II) and nickel(II). The sorbents were synthesized from a mixture of linear low molecular weight polyethyleneimine oligomers. The composition, structure and distribution of complexes in the resin phase were investigated. The effects of the synthesis conditions, loading degree and water content were examined. The presence of certain copper complexes was found to be a convenient characteristic of the imprinting efficiency. The optimum synthesis conditions for obtaining sorbents imprinted with copper(II) or nickel(II) were identified. The imprinting results in the improvement of the stability of the complexes and the selectivity and working capacity of the sorbents. The imprinted samples are also characterized by a more even distribution of chelating sites. The synthesis conditions and loading by ions allow for the regulation of the ratio between individual complexes and magnetic associates in the resin phase. This is a critical point on the future use of the metal containing imprinted sorbents as catalysts. (C) 2003 Published by Elsevier Science Ltd

Signatures of Electronic Correlations in Optical Properties of LaFeAsO1−x_{1-x}Fx_x

Spectroscopic ellipsometry is used to determine the dielectric function of the superconducting LaFeAsO$_{0.9}$F$_{0.1}$ ($T_c$ = 27 K) and undoped LaFeAsO polycrystalline samples in the wide range 0.01-6.5 eV at temperatures 10 $\leq T \leq$ 350 K. The free charge carrier response in both samples is heavily damped with the effective carrier density as low as 0.040$\pm$0.005 electrons per unit cell. The spectral weight transfer in the undoped LaFeAsO associated with opening of the pseudogap at about 0.65 eV is restricted at energies below 2 eV. The spectra of superconducting LaFeAsO$_{0.9}$F$_{0.1}$ reveal a significant transfer of the spectral weight to a broad optical band above 4 eV with increasing temperature. Our data may imply that the electronic states near the Fermi surface are strongly renormalized due to electron-phonon and/or electron-electron interactions.Comment: 4 pages, 4 figures, units in Fig.2 adde

Low-energy Mott-Hubbard excitations in LaMnO_3 probed by optical ellipsometry

We present a comprehensive ellipsometric study of an untwinned, nearly stoichiometric LaMnO_3 crystal in the spectral range 1.2-6.0 eV at temperatures 20 K < T < 300 K. The complex dielectric response along the b and c axes of the Pbnm orthorhombic unit cell, \epsilon^b(\nu) and \epsilon^c(\nu), is highly anisotropic over the spectral range covered in the experiment. The difference between \epsilon^b(\nu) and \epsilon^c(\nu) increases with decreasing temperature, and the gradual evolution observed in the paramagnetic state is strongly enhanced by the onset of A-type antiferromagnetic long-range order at T_N = 139.6 K. In addition to the temperature changes in the lowest-energy gap excitation at 2 eV, there are opposite changes observed at higher energy at 4 - 5 eV, appearing on a broad-band background due to the strongly dipole-allowed O 2p -- Mn 3d transition around the charge-transfer energy 4.7 eV. Based on the observation of a pronounced spectral-weight transfer between low- and high-energy features upon magnetic ordering, they are assigned to high-spin and low-spin intersite d^4d^4 - d^3d^5 transitions by Mn electrons. The anisotropy of the lowest-energy optical band and the spectral weight shifts induced by antiferromagnetic spin correlations are quantitatively described by an effective spin-orbital superexchange model. An analysis of the multiplet structure of the intersite transitions by Mn e_g electrons allowed us to estimate the effective intra-atomic Coulomb interaction, the Hund exchange coupling, and the Jahn-Teller splitting energy between e_g orbitals in LaMnO_3. This study identifies the lowest-energy optical transition at 2 eV as an intersite d-d transition, whose energy is substantially reduced compared to that obtained from the bare intra-atomic Coulomb interaction.Comment: 10 pages, 14 figure

Spin-controlled Mott-Hubbard bands in LaMnO_3 probed by optical ellipsometry

Spectral ellipsometry has been used to determine the dielectric function of an untwinned crystal of LaMnO_3 in the spectral range 0.5-5.6 eV at temperatures 50 K < T < 300 K. A pronounced redistribution of spectral weight is found at the Neel temperature T_N = 140 K. The anisotropy of the spectral weight transfer matches the magnetic ordering pattern. A superexchange model quantitatively describes spectral weight transfer induced by spin correlations. This analysis implies that the lowest-energy transitions around 2 eV are intersite d-d transitions, and that LaMnO_3 is a Mott-Hubbard insulator.Comment: 4 pages, 4 figure

Infrared studies of a La_(0.67)Ca_(0.33)MnO_3 single crystal: Optical magnetoconductivity in a half-metallic ferromagnet

The infrared reflectivity of a La_(0.67)Ca_(0.33)MnO_3 single crystal is studied over a broad range of temperatures (78–340 K), magnetic fields (0–16 T), and wave numbers (20–9000cm^(-1)). The optical conductivity gradually changes from a Drude-like behavior to a broad peak feature near 5000cm-1 in the ferromagnetic state below the Curie temperature T_C=307K. Various features of the optical conductivity bear striking resemblance to recent theoretical predictions based on the interplay between the double exchange interaction and the Jahn-Teller electron-phonon coupling. A large optical magnetoconductivity is observed near T_C

Infrared Studies of a La_{0.67}Ca_{0.33}MnO_3 Single Crystal: Optical Magnetoconductivity in a Half-Metallic Ferromagnet

The infrared reflectivity of a $\rm La_{0.67}Ca_{0.33}MnO_3$ single crystal is studied over a broad range of temperatures (78-340 K), magnetic fields (0-16 T), and wavenumbers (20-9000 cm$^{-1}$). The optical conductivity gradually changes from a Drude-like behavior to a broad peak feature near 5000 cm$^{-1}$ in the ferromagnetic state below the Curie temperature $T_C=307 K$. Various features of the optical conductivity bear striking resemblance to recent theoretical predictions based on the interplay between the double exchange interaction and the Jahn-Teller electron-phonon coupling. A large optical magnetoconductivity is observed near $T_C$.Comment: 4 pages, 4 figures, Latex, PostScript; The 7th Joint MMM-Intermag Conference,San Francisco, January 6-9, 1998; The Int. Conf. on Strongly Correlated Electron Systems, Paris, July 15-18,199

Quality flags for GSP-Phot Gaia DR3 astrophysical parameters with machine learning: Effective temperatures case study

Gaia Data Release 3 (DR3) provides extensive information on the astrophysical properties of stars, such as effective temperature, surface gravity, metallicity, and luminosity, for over 470 million objects. However, as Gaia's stellar parameters in GSP-Phot module are derived through model-dependent methods and indirect measurements, it can lead to additional systematic errors in the derived parameters. In this study, we compare GSP-Phot effective temperature estimates with two high-resolution and high signal-to-noise spectroscopic catalogues: APOGEE DR17 and GALAH DR3, aiming to assess the reliability of Gaia's temperatures. We introduce an approach to distinguish good-quality Gaia DR3 effective temperatures using machine-learning methods such as XGBoost, CatBoost and LightGBM. The models create quality flags, which can help one to distinguish good-quality GSP-Phot effective temperatures. We test our models on three independent datasets, including PASTEL, a compilation of spectroscopically derived stellar parameters from different high-resolution studies. The results of the test suggest that with these models it is possible to filter effective temperatures as accurate as 250 K with ~ 90 per cent precision even in complex regions, such as the Galactic plane. Consequently, the models developed herein offer a valuable quality assessment tool for GSP-Phot effective temperatures in Gaia DR3. Consequently, the developed models offer a valuable quality assessment tool for GSP-Phot effective temperatures in Gaia DR3. The dataset with flags for all GSP-Phot effective temperature estimates, is publicly available, as are the models themselves.Comment: 13 pages, 10 figure

Influence of wire geometry on the mechanical behavior of the TiNi design

The present article is aimed at studying the deformation behavior of TiNi wire and knitted metal TiNi mesh under uniaxial tension and revealing the role of wire geometry on their main mechanical characteristics and mechanisms of deformation behavior. The temperature dependence curve of the electrical resistance indicates that a two-stage martensitic transformation of B2!R!B190 is occurring, and is responsible for the superelasticity effect. The TEM results showed that at room temperature, the TiNi wire has a nanocrystalline structure composed of B2 austenite grains. A change in the deformation mechanism was established under the uniaxial tension, where the TiNi wire exhibits the effect of superelasticity, while the knitted metal TiNi mesh made from this wire is characterized by hyperelastic behavior. Fracturing of the knitted metal TiNi mesh requires significant loads of up to 3500 MPa compared to the fracture load of the TiNi wire. With the uniaxial tension of the wire, which maximally repeats the geometry of the wire in knitted metal mesh, an increase in mechanical characteristics was observed