Spectroscopic and E. P. R Studies of the Crystal and Molecular Structure of Cu(2-Benzoylpyridine)2(NO3)2.H2O

Abstract

Solid Cu(2-Benzoylpyridine)₂(NO₃)₂ has been studied by UV-Vis, IR, and EPR (X-band, Q-band) techniques. Monoclinic crystal symmetry was determined with two molecules per unit cell. Copper (II) is coordinated by two benzoylpyridine ligands and a single NO₃ group in the chromophore CuN₂O₃ of distorted trigonal bypiramidal stereochemistry. Exchange coupling values were determined from EPR spectra as |J| = 0.0026(2) cm^?1 between magnetically nonequivalent copper (II) sites, and |J| < O.3 cm^?1 between equivalent sites.

Results are discussed by a comparison with Cu(II)-benzoyl-pyridine complexes coordinated with azide N₃ ^? anions.     

The influence of the activator concentration on electroluminescence properties of thin layers in a system ZnS: Cu,Mn, Cl

The influence of activators, especially copper, on the electric properties of vacuum-evaporated electroluminescent layers excited by dc voltage is investigated. In the course of the “one step” method of preparation, non-uniform incorporation of the activators occurs. The layers are divided into three groups according to the copper concentration. 1 — “low” (1×10^?3 g Cu/g ZnS) with the emission stimulated at Al^? electrode, 2 — “medium” (5–8×10^?3 g Cu/g ZnS) with the emission at both polarities, 3 — “high” (9×10^?3?5×10^?2 g Cu/g ZnS) with the emission at Al⁺ electrode. Layers in these groups differ not only in their electrical properties and in the existence of the forming process but they have also various distribution of the light-emitting regions. The light emission has been found in the intermediate regions between the microcrystalline grains as well as on the interface between the microcrystalline grain and ZnS phosphor phase. According to structural properties the light emission originates from microcrystalline grains too.     

Beta-induced reduction in Cu/Si-structure adhesion

The effect of low-flux (I ～ 1.8 × 10⁵ cm^?2 s^?1) β irradiation on the process of the delamination of thin copper films (with a thickness of ～100 nm) from a silicon substrate under indentation by a Berkovich pyramid is studied. It is revealed that irradiation with a fluence of F = 3.24 × 10¹⁰ cm^?2 leads to an increase in the perimeter and area of the copper-film delaminations formed upon penetration of the indenter. This indicates a β-induced reduction in adhesion in the Cu/Si structure.     

ESR study of exchange coupled pairs in copper diethyldithiocarbamate

ESR investigations on exchange coupled pairs of Cu ions in single crystals of Cu(dtc)₂, isomorphously diluted with the corresponding diamagnetic zinc salt, are reported. The spin Hamiltonian parameters for the coupled species (S=1) are:g _‖=2.1025,g ₊=2.031,A=75.1×10⁻⁴ cm⁻¹,B=14.8×10⁻⁴,D=276.0×10⁻⁴ cm⁻¹ andE=46.7×10⁻⁴ cm⁻¹. While theg andA tensors show tetragonal symmetry, the zeor-field splitting tensor is rhombic and has principal axes different from those of theg andA tensors. Intensity measurements made down to 4.2 K indicate that the exchange is ferromagnetic with |FFF| ∼ 10 cm⁻¹. Direct dipole-dipole interaction appears to be the major contribution to the zero-field splitting. A calculation on the distributed point dipole model shows that dipolar interaction is considerably modified by the high covalency of the Cu-S bond and accounts for the rhombic nature of the tensor. The possible exchange mechanisms in Cu(dtc)₂—direct exchange and superexchange through the bridging sulphurs—are discussed.     

Brillouin scattering observation of phonon renormalization in KC1:CN−

The phonon-defect interaction in KC1:CN^? has been studied in the 16 GHz frequency range using the Brillouin scattering technique. Brillouin spectra of KC1:CN^? at 4.2 K show a defect induced phonon velocity renormalization. The measurements are consistent with a 〈111〉 oriented CN^? dipole in KC1 with a tunneling level of T_2g symmetry at 2.6 cm^?1 and a coupling constant of 1.5 × 10^?21 cm³.     

Laser induced modulation of optical absorption in ZnSe

Laser pulses generate electron-hole pairs in a ZnSe crystal and selective trapping alters the carrier concentration. A result is modulated optical absorption Δα, probed by a second monochromatic beam. The effect is extrinsic and may be associated with ionized Cu in substitution for Zn. Phase-sensitive kinetics measurements reveal a thermal component and indicate that at least two impurity levels are involved, the latter with photon-capture cross sections q in the range 0.3 × 10^?16 to 0.9 × 10^?16cm², corresponding to non-equilibrium carrier concentrations Δn?10¹³cm^?3.     

Theoretical integrated intensities for the 2ν2 and 2ν2-ν2 bands of HCN and DCN

Dipole moment functions, both perpendicular and parallel to the molecular axis, are calculated from the SCF and MRD-CI results of a previous study for the normal ν₂ bending vibrations of HCN and DCN. Vibrationally averaged dipole moments and the infrared transition matrix elements are then obtained from the dipole moment functions and vibrational wave functions. MRD-CI results, with known experimental values in parentheses, for HCN are 〈0|μ|0〉 = ?2.954(?2.985) D, 〈1|μ|1〉 = ?2.915(±2.942) D, 〈0|μ|1〉 = 0.148(0.147) D, 〈0|μ|2〉 = ?0.027 D, 〈1|μ|2〉 = 0.210 D. Calculated absolute intensities at 1 atm and 0°C for the (02⁰0) ← (000), (02⁰0) ← (010), and (02²0) ← (010) bands of HCN are 25 (40 ± 10 as estimated from spectra), 8.5, and 17.0 atm^?1 cm^?2, respectively. Results for DCN are also reported.     

Interactions of CO molecules adsorbed on oxidised Cu(111) and Cu(110)

Reflection absorption infrared spectroscopy has been used in conjunction with LEED and surface potential measurements to study low temperature CO adsorption on the oxidised Cu surfaces Cu(111)O|$\text{3}\text{2}\text{?}\text{2}$|, Cu(110)O(2 × 1) and Cu(110)Oc(6 × 2). On all three surfaces adsorption at 80 K yields surface potential changes in excess of 0.6 V and does not lead to the formation of an ordered overlayer. At high coverages the adsorption enthalpy is lower than on the clean surfaces. Infrared spectra show the growth of a doublet band with components initially at 2100 and 2117 cm^?1 on the oxidised Cu(111) surface. Similar features seen on the oxidised Cu(110) surfaces are accompanied by a band at 2140 cm^?1: a very weak band at the same frequency on oxidised Cu(111) is attributed to defect sites. Studies of the temperature dependence of the spectrum from oxidised Cu(111) lead to the conclusion that two different binding sites are occupied. Spectra of ${}^{12}\text{CO}{}^{13}\text{CO}$ mixtures show that the molecules occupying these sites are in close proximity to each other, and that the spectrum is subject to large but opposing coverage-dependent frequency shifts.     

Theoretical calculation of the dipole moment function of the a4Π state of NO

The potential energy curve and theoretical dipole moment function of the a⁴Π state of NO have been determined using full-valence and first-order configuration interaction wavefunctions. Using these two different wavefunctions, the dipole moments of the a⁴Π, v = 3 level have been found equal, respectively, to 0.16 D and 0.30 D, with the polarity N⁺O^?. These values compare well with the value of |0.20 ± 0.04| D determined by Lisy and Klemperer. The first derivative of the dipole moment has also been calculated to be equal to 1.25–1.73 D/bohr.     

Photoluminescent studies of the condensed phase in phosphorus-doped silicon

Photoluminescent studies give evidence for the existence of the electron—hole droplet in phosphorus-doped silicon in the impurity concentration range 9.0 × 10¹⁵cm^?3 ? N_D ? 4.3 × 10¹⁹cm^?3.     

Continuous-Wave and Time-Resolved Electron Paramagnetic Resonance Study of Dimerized Aza-Crown Copper Porphyrins

The dimerization of 5-(4’-(aza-15-crown-5)-phenyl) copper porphyrin (CuP) upon the addition of the K(SCN) salt to a solution of the CuP monomer has been proven by electron paramagnetic resonance (EPR). The magnetic resonance parameters of the CuP monomer, the exchange interaction parameter, J = +0.25 cm^?1, and the Cu–Cu distance of the CuP dimer have been determined by comparing the experimental continuous-wave EPR spectra with the results of the numerical calculations. The photoexcited states have been studied in the time-resolved EPR experiments. It has been shown that the time-resolved EPR spectra of the dimerized porphyrins can be presented as a sum of two components that represent the spectra derived by integrating the dataset in the time windows of 1.1–1.3 and 2.1–2.3 μs. To describe the spectrum in the time window of 2.1–2.3 μs, it is assumed that there is an essential contribution to the signal from the excited state of the supramolecule, which is formed by the interaction between the photoexcited porphyrin in the quartet state and the neighboring non-excited porphyrin in the ground state.     

EPR of an exchange-coupled,hydrogen-bridged one-dimensional Cu(II) complex containing both octahedral and square pyramidal geometries in the same unit cell

Single-crystal X and Q band EPR of a hydrogen-bridged l-dimensional Cu(II) complex, [Cu(stpy)₂(CH₃COO)₂(H₂O)₂] [CU(stpy)₂(CH₃COO) ₂(H₂O)], containing both octahedral and square pyramidal geometries in the same unit cell, has been studied at 300 K. EPR of powder samples at X band frequencies at 300 K and 77 K show exchange-narrowed resonance. The peak-to-peak linewidths of the signals are 80 G and 85 G, respectively. However, at Q band frequencies it exhibits an axially symmetric spectrum with spin Hamiltonian parameters g_|| = 2.303 and g_⊥ = 2.077, corresponding to an |x² ? y²〉 ground state. Single-crystal X band EPR spectra show a single resonance line for all the orientations, indicating the complex to be in the strong exchange regime. On the other hand, Q band spectra exhibit two lines corresponding to the weak exchange regime. An estimate of the interchain-site exchange coupling constant J′ = 0.0125(3) cm^?1 also reveals weak coupling between the magnetically distinct Cu(II) centres. The ratio of J′/J = 8.25 × 10^?2 is low enough to make the interactions almost l-dimensional, in agreement with X-ray data. EPR linewidth and lineshape analyses also support l-dimensional behaviour of the system.     

α-Al2O3单晶中Fe3+离子的电子顺磁共振

本文对α-Al₂O₃单晶体中Fe³⁺离子在室温下,X波段进行了电子顺磁共振研究,发现Fe³⁺离子实际上占据四种磁性不等价晶位。在同一氧离子层间的两种晶位上的Fe³⁺离子具有相同的自旋哈密顿参量,而不同氧离子层间的晶位上的Fe³⁺离子具有不同的自旋哈密顿参量,两种自旋哈密顿参量为:(1)g_‖=2.001,g_⊥=2.003,D=1679 关键词：     

The relaxation rate of the magnetic moment of a shallow acceptor center as a function of impurity concentration in silicon

A study is made into the temperature dependence of residual polarization of negative muons in crystalline silicon with the concentration of impurity of the n-and p-types ranging from 8.7×10¹³ to 4.1× 10¹⁸ cm^?3. The measurements are performed in a magnetic field of 1000 G transverse to the muon spin, in the temperature range from 4.2 to 300 K. The form of the temperature dependence of the relaxation rate v of the magnetic moment of the μAl⁰ acceptor in silicon is determined. For a nondegenerate semiconductor, the relaxation rate depends on temperature as v ∝ T ^q (q ≈ 3). A variation in the behavior of the temperature dependence and a multiple increase in the relaxation rate are observed in the range of impurity concentration in excess of 10¹⁸ cm^?3. The importance of phonon scattering and spin-exchange scattering of free charge carriers by an acceptor from the standpoint of relaxation of the acceptor magnetic moment is discussed. The constant of hyperfine interaction in an acceptor center formed by an atom of aluminum in silicon is estimated for the first time: |A _hf (Al)/2π| ～ 2.5×10⁶s^?1.     

Hyperfine and nuclear quadrupole interactions in copper-doped cadmium oxalate trihydrate single crystals

Electron spin resonance experiments on Cu²⁺ doped in a single crystal of cadmium oxalate trihydrate grown by a slow diffusion technique have been carried out at 77 K. The major features of the ESR spectra can be attributed to divalent copper (3d⁹) in substitutional Cd²⁺ sites. Information has been gained about the hyperfine and quadrupole interactions concerning the ion. The spin-Hamiltonian parameters in the $\text{S =}\text{1}\text{2}$, $\text{I =}\text{3}\text{2}$ manifold are: g_x = 2.0211; g_y = 2.2249; g_z = 2.4536; A_x = +84.5 × 10^?4cm^?1; A_y = +16.8 × 10^?4cm^?1; $\text{A}{}_{\mathrm{z}}\text{= ?40.8 × 10 ×}{}^{\mathrm{?4}}\text{cm}{}^{\mathrm{?1}}$; P_x = ?7.4 × 10^?4cm^?1; P_y = ?0.4 × 10^?4cm^?1; and P_z = +7.8 × 10^?4cm^?1. An evaluation of the asymmetry and quadrupole coupling parameters revealed that the ground state of the guest ion in Cd(COO)₂ · 3H₂O is 0.97|x² ?y₂ > +0.24 |3z² ? r² >.     

The moment of inertia of the proto neutron star PSR J0348+0432 under neutrino trapped

The moment of inertia of the proto neutron star PSR J0348+0432 is studied in the framework of relativistic mean field theory under neutrino trapped. We find that the temperature of the PNS PSR J0348+0432 increases with the increase of the baryon number density and at the center of the star it is in the range T_c = 41.662–45.685 MeV. Corresponding to the observation mass 1.97–2.05 M_⊙, the radius of the NS PSR J0348+0432 is in the range 12.948–12.16 km whereas that of the PNS PSR J0348+0432 is in the range 14.46–13.561 km. The radius of the PNS PSR J0348+0432 has increased by 11.7%–11.5% compared with that of the NS PSR J0348+0432. The central moment of inertia of the PNS PSR J0348+0432 is in the range 2.207?×?10⁴⁵–1.914?×?10⁴⁵ g cm² whereas that of the NS PSR J0348+0432 is only in the range 1.9?×?10⁴⁵–1.552?×?10⁴⁵ g cm². Compared with the moment of inertia of the NS PSR J0348+0432, the central moment of inertia of the PNS PSR J0348+0432 increases by 16%–23%.     

New measurements of the neutron electric dipole moment

We report a new measurement of the neutron electric dipole moment with the PNPI EDM spectrometer using the ultracold neutron source PF2 at the research reactor of the ILL. Its first results can be interpreted as a limit on the neutron electric dipole moment of |d _n | < 5.5 × 10^?26 e cm (90% confidence level).     

In situ X‐ray absorption spectroscopic studies of copper in a copper‐rich sludge during electrokinetic treatments

Speciation of copper in a copper‐rich chemical‐mechanical polishing sludge during electrokinetic treatment has been studied by in situ extended X‐ray absorption fine structure (EXAFS) and X‐ray absorption near‐edge structure (XANES) spectroscopy. The least‐squares‐fitted XANES spectra indicate that the main copper species in the sludge are Cu(OH)₂ (74%), nanosize CuO (20–60 nm) (13%) and CuO (>100 nm) (13%). The average bond distance and coordination number (CN) of Cu—O are 1.96 Å and 3.5, respectively. Under electrokinetic treatment (5 V cm^?1) for 120 min, about 85% of the copper is dissolved in the electrolyte, 13% of which is migrated and enriched on the cathode. Notably the copper nanoparticles in the sludge can also migrate to the cathode under the electric field. By in situ EXAFS, it is found that during the electrokinetic treatment the bond distance and CN of Cu—O are increased by 0.1 Å and 0.9, respectively.     

Correlation of plume dynamics and oxygen pressure with VO2 stoichiometry during pulsed laser deposition

Vanadium dioxide thin films have been deposited on Corning glass substrates by a KrF laser ablation of V₂O₅ target at the laser fluence of 2 J?cm^?2. The substrate temperature and the target-substrate distance were set to 500 ^°C and 4 cm, respectively. X-ray diffraction analysis showed that pure VO₂ is only obtained at an oxygen pressure range of 4×10^?3–2×10^?2 mbar. A higher optical switching contrast was obtained for the VO₂ films deposited at 4×10^?3–10^?2 mbar. The films properties were correlated to the plume-oxygen gas interaction monitored by fast imaging of the plume.     

EPR, Optical Absorption and Superposition Model Study of Fe3+-Doped Ammonium Dihydrogen Phosphate Single Crystals

X-band electron paramagnetic resonance (EPR) studies are carried out on Fe³⁺ ions doped in ammonium dihydrogen phosphate (ADP) single crystals at room temperature. The crystal field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations. The obtained values of spin Hamiltonian and zero-field parameters of the Fe³⁺ ion in ADP are: g = 1.994 ± 0.002, |D| = (220 ± 5) × 10^?4 cm^?1 and a = (640 ± 5) × 10^?4 cm^?1. On the basis of EPR data, the site symmetry of the Fe³⁺ ion in the crystal is discussed. The Fe³⁺ ion enters the lattice substitutionally replacing the NH₄ ⁺ sites. The optical absorption of the crystal is also studied at room temperature in the wavelength range of 195–925 nm. The energy values of different orbital levels are calculated. The observed bands are assigned as transitions from the ⁶ A _1g (S) ground state to various excited quartet levels of the Fe³⁺ ion in a cubic crystalline field. From the observed band positions, Racah interelectronic repulsion parameters (B and C), cubic crystal field splitting parameter (D _q ) and Trees correction are calculated. There values are: B = 970, C = 1,923, D _q  = 1,380 cm^?1 and α = 90 cm^?1, respectively. On the basis of EPR and optical data, the nature of bonding in the crystal is discussed. The zero-field splitting (ZFS) parameters are also determined theoretically using B _kq parameters estimated from the superposition model. The values of ZFS parameters thus obtained are |D| = (213 ± 5) × 10^?4 cm^?1 and |E| = (21 ± 5) × 10^?4 cm^?1.