常温下YGaG:Fe3+体系的EPR谱研究

本文采用对角化三角晶场中d5组态离子的完全能量矩阵的方法,研究了YGaG:Fe3 体系的EPR谱与局域晶格畸变的关系,利用EPR谱的低对称参量D和(a-F)的实验值确定出Fe3 离子在YGaG:Fe3 体系中的键长R=0.2005 nm,键角θ=51.498°,以及晶格畸变角Δθ=0.954°。     

EPR and Optical Absorption Study of Cr3+-Doped Dipotassium Tetrachloropalladate

X-band electron paramagnetic resonance (EPR) study of Cr³⁺-doped dipotassium tetrachloropalladate single crystal is done at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters have been evaluated by employing hyperfine resonance lines observed in EPR spectra for different orientations of crystal in externally applied magnetic field. The values of spin-Hamiltonian and zero-field splitting (ZFS) parameters of Cr³⁺ ion-doped DTP for site I are: g _x  = 2.096 ± 0.002, g _y  = 2.167 ± 0.002, g _z  = 2.220 ± 0.002, D = (89 ± 2) × 10^?4 cm^?1, E = (16 ± 2) × 10^?4 cm^?1. EPR study indicates that Cr³⁺ ion enters the host lattice substitutionally replacing K⁺ ion and local site symmetry reduces to orthorhombic. Optical absorption spectra are recorded at room temperature. From the optical absorption study, the Racah parameters (B = 521 cm^?1, C = 2,861 cm^?1), cubic crystal field splitting parameter (Dq = 1,851 cm^?1) and nephelauxetic parameters (h = 2.06, k = 0.21) are determined. These parameters together with EPR data are used to discuss the nature of bonding in the crystal.     

EPR, Optical Absorption and Superposition Model Studies of Fe3+-Doped Diammonium Hexaaqua Magnesium Sulfate: A Case of Hyperfine Structure

An electron paramagnetic resonance (EPR) study of Fe³⁺-doped diammonium hexaaqua magnesium sulphate single crystal is carried out at liquid nitrogen temperature. EPR spectrum shows two sites. The spin-Hamiltonian parameters are evaluated from angular variation of observed hyperfine lines. Fe³⁺ ion enters the host lattice substitutionally at site I, replacing Mg²⁺, whereas it enters interstitially at site II. The local site symmetry of Fe³⁺ ion within the host lattice is orthorhombic. An optical absorption study is performed at room temperature. Using the optical absorption spectrum the bands are assigned and the Racah parameters (B and C) and cubic crystal field splitting parameter Dq are determined. The nature of metal–ligand bonding in the crystal is determined using EPR and optical data. Crystal field parameters and zero-field splitting parameters (ZFSPs) are evaluated theoretically for both the sites using superposition model and microscopic spin Hamiltonian together with perturbation equations, respectively. The theoretically evaluated ZFSPs are in good agreement with the experimental values.     

EPR,optical and superposition model study of Mn2+ doped L+ glutamic acid

Electron paramagnetic resonance (EPR) study of Mn²⁺ doped L+ glutamic acid single crystal is done at room temperature. Four interstitial sites are observed and the spin Hamiltonian parameters are calculated with the help of large number of resonant lines for various angular positions of external magnetic field. The optical absorption study is also done at room temperature. The energy values for different orbital levels are calculated, and observed bands are assigned as transitions from ⁶A_1g(s) ground state to various excited states. With the help of these assigned bands, Racah inter–electronic repulsion parameters B = 869 cm^?1, C = 2080 cm^?1 and cubic crystal field splitting parameter Dq = 730 cm^?1 are calculated. Zero field splitting (ZFS) parameters D and E are calculated by the perturbation formulae and crystal field parameters obtained using superposition model. The calculated values of ZFS parameters are in good agreement with the experimental values obtained by EPR.     

The interpretation of the crystal field groundstate of Dy3+ in Pd

A recent interpretation of the crystal field ground state of Dy³⁺ in Pd is discussed in terms of a model where isotropic conduction electron/ion exchange is included. The new results suggest the ratio of fourth and sixth order crystal field parameters to be 292±4. The magnitude of the crystal field parameters cannot be determined. A resonance originating possibly from Dy ions in non-cubic sites is identified.     

Elektrische Quadrupolwechselwirkungen von20F im MgF2-Einkristall

Polarized²⁰F nuclei (T _1/2=11s,I=2) have been produced in a tetragonal MgF₂ single crystal by capture of polarized neutrons. Nuclear magnetic resonance transitions have been induced and observed via the asymmetricΒ decay to²⁰Ne, yielding the quadrupole coupling constant ¦e ² q Q/h¦=5.77(2)MHz, the quadrupole moment ¦Q(²⁰F)¦=0.064(12) b and the asymmetry parameter of the electric field gradientη=0.317(2). In order to study possible lattice defects produced by the recoil displacement due to the captureγ-rays NMR signals were registered both at room temperature and at 12 K. Width and depth of the resonance curves indicated that at room temperature nearly all²⁰F ions occupy normal lattice sites with an undisturbed environment. At 12 K, however, where no annealing occurs, this is only true for about half of the²⁰F ions which are stopped directly at defect free sites. The other half of the²⁰F ions at 12 K shows resonance frequencies shifted by defect interactions up to the order of some 100 kHz. Furthermore two simple methods are reported which allow a quick estimate of the strength of the quadrupolar interaction: (1) observation of theΒ decay asymmetry versus the magnetic field strength (decoupling curve), (2) broad-band modulation of the inducedrf field and observation of theΒ asymmetry versus the depth of the modulation.     

Dynamic magnetic properties of Ising graphene-like monolayer

Dynamic magnetic properties of the mixed-spin (3/2, 5/2) Ising graphene-like monolayer in an oscillating magnetic field are studied by means of Monte Carlo simulation. The effects of Hamiltonian parameters such as crystal field and time-dependent oscillating magnetic field on the dynamic order parameter, susceptibility and internal energy of the system are well presented and explained. Moreover, much attention has also been dedicated to the phase diagrams with different parameters in order to better comprehend the impacts of these parameters on the critical temperature. Our results reveal that the crystal fields of two sublattices have similar effects on the critical temperature, but the bias field and amplitude of oscillating field have opposite effects on it. We hope that our research can be of guiding significance to the theoretical and experimental studies of graphene-like monolayer.     

EPR,optical absorption and superposition model studies of Fe3+-doped cesium chloride single crystals: a case of substitutional as well as interstitial sites

An electron paramagnetic resonance study of Fe³⁺-doped cesium chloride single crystals was carried out at room temperature. Three sites are observed. The spin Hamiltonian parameters were determined from the angular variation of the observed resonance lines. The hyperfine structure is observed due to the presence of Fe⁵⁷ centers. At site I, Fe³⁺ enters the lattice substitutionally, replacing Cs⁺ in the cubic symmetry of the crystal, whereas at sites II and III, Fe³⁺ enters the lattice interstitially. The local site symmetry of Fe³⁺ in the host lattice is considered to be orthorhombic. An optical absorption study of the crystal was also performed at room temperature. The observed bands were assigned and the Racah inter-electronic repulsion parameters (B and C) and the cubic crystal field splitting parameter (Dq) were determined. On the basis of EPR and optical data, the nature of the metal–ligand bonding in the crystal was determined. The crystal field parameters were evaluated using the superposition model and then used in the microscopic spin Hamiltonian and perturbation equations to determine the zero-field splitting parameters (ZFSPs) theoretically for all sites observed. The theoretical ZFSPs are in good agreement with the experimental values.     

EPR and Optical Absorption Studies of VO2+-Doped Diammonium Hexaaqua Magnesium(II) Sulfate

Electron paramagnetic resonance (EPR) studies of VO²⁺ impurity ion in single crystals of diammonium hexaaqua magnesium(II) sulfate are carried out at 9.5 GHz (X-band) at room temperature. Different spin-Hamiltonian parameters are determined. VO²⁺ is expected to enter the lattice substitutionally. Superhyperfine splitting is also observed. An EPR study of a powder sample is done that supports the data obtained from single crystal studies. Optical absorption studies are also performed at room temperature. The crystal field parameter (D_q), tetragonal parameters (D_s and D_t), and various bonding parameters are evaluated to estimate the covalency and nature of bonding of VO²⁺ with its different ligands.     

Crystal field parameters and phase transitions in ErSb

The crystal field levels of the Er ($\text{J =}\text{15}\text{2}$) ion in a single crystal of ErSb have been measured by inelastic neutron scattering. The crystal field parameters obtained by a least squares fit to the spectra at several temperatures are: B₄ = (0·473 ± 0·005) × 10^?2°K and B₆ = (0·59 ± 0·06) × 10^?5°K, which differ considerably from the values o by interpolation from measurements on other compounds. In addition the temperature dependence of the magnetic scattering in the vicinity of the Néel temperature (T_N = 3·55°K) clearly demonstrates that the transition is second order in contrast to the first order behavior suggested by specific heat measurements. Also, any lattice distortion accompanying the magnetic ordering is less than 0.1 per cent, the resolution of the present experiment.     

Electron paramagnetic resonance of Cr3+ ions in ferroelastic CsLiSO4

The X-band EPR studies of Cr³⁺-doped LCS have been performed. The values of the spin-Hamiltonian parameters for Cr³⁺ ions have been estimated at room temperature. The effect of crystal twinning on the EPR spectra has also been described. The temperature behaviour of EPR lines originated from two structurally different chromium complexes has been studied close to the ferroelastic phase transition. From the temperature dependence of positions of the split resonance lines a value of the critical exponent β of the order parameter was found to be β = 0.25.     

Extended triplet excitons in K+TCNQ−

By means of ESR, two types of triplet excitons have been discovered in K⁺TCNQ^? crystals, corresponding to the two independent rows of TCNQ^? ions in the crystal structure of this compound. The orientational dependence of the dipolar splittings at ?46°C and intensity measurements as a function of temperature are presented. The zero field splitting parameters are small and therefore the excitons must be large with respect to a lattice parameter. The extended nature of the excitons indicates, that either the electron electron repulsions are relatively small with respect to the one electron bandwidth in this material or that the alternation of the interionic distances is small.     

Crystal fields of Pr in LiYF4 under pressure

Fluorescence spectra of LiYF₄:Pr³⁺ have been measured between 12,000 and 22,000 cm⁻¹ under pressures up to 10 GPa. In total, 25 crystal field energy levels were obtained and used for the determination of free-ion and crystal field parameters under pressure. According to the nephelauxetic effect, the free-ion parameters decrease with increasing pressure. The relative decrease is larger for the Slater than for the spin-orbit coupling parameter. This behavior is consistent with former studies on Pr³⁺ in different crystals and can be explained by a special covalency model. According to an effective D_2d symmetry, five crystal field parameters B₀²(f,f), B₀⁴(f,f), B₄⁴(f,f), B₀⁶(f,f), and B₄⁶(f,f) are non-zero. The pressure-induced changes of these parameters have been determined up to the maximum pressure of 10 GPa. In order to improve the calculation of the crystal field levels, the configuration interactions with the 4f¹6p¹ configuration have been taken into account. The effect of these interactions are also analyzed under pressure and distinct improvements of the energy level calculations have been obtained.     

BEEM-π calculations for a series of pyridines and their 14N N.Q.R.

The ⁵⁷Fe Mössbauer spectrum of a powdered sample of phthalocyanine-iron(II) in an applied magnetic field of 3·0 teslas has been measured as a function of temperature in the range 4·2 K to 100 K. Measurements have also been made at 4·2 K with 6·0 teslas applied, and on a single crystal specimen at 4·2 K with 3·0 teslas applied. Independent computer fits to the three measurements taken at 4·2 K were found to be consistent with one another, and showed that detailed information concerning magnetic anisotropy can be obtained even from powdered samples of paramagnets by Mössbauer spectroscopy. Although the asymmetry parameter in the electric field gradient tensor was found to be small, there was a significant departure from tetragonal symmetry in the magnetic properties of the molecule. The magnetic hyperfine field at the ⁵⁷Fe nucleus was found to be positive in all directions, indicating that all three electronic g values are significantly greater than 2·0.     

EPR and optical studies of Cu doped ammonium dihydrogen phosphate single crystals

Electron paramagnetic resonance (EPR) spectra of Cu²⁺ ion in ammonium dihydrogen phosphate are studied at liquid nitrogen temperature (77 K). Four magnetically inequivalent Cu²⁺ sites in the lattice are identified. The angular variation spectra of the crystal in the three orthogonal planes indicate that the paramagnetic impurity, Cu²⁺ enters the lattice substitutionally in place of NH₄⁺ ions. The spin Hamiltonian parameters are determined with the fitting of spectra to rhombic symmetry crystalline field. The ground state wave function of Cu²⁺ ion is constructed and found to be predominantly |x²-y²〉. The cubic field parameter (Dq) and tetragonal parameters (Ds and Dt) are determined from optical spectra at room temperature. By correlating EPR and optical absorption spectra, the bonding coefficients are calculated and nature of bonding of metal ion with different ligands in the crystal is discussed.     

低温高压下的Na5Eu(WO4)4的发光和晶体场参数

用低温金刚石对顶砧高压显微光谱系统在20—300K低温和0—10GPa高压范围内研究了白钨矿型化学计量的基质发光晶体四钨酸铕钠Na₅Eu(WO₄)₄中Eu³⁺的发光.确定了Eu³⁺荧光谱线和能级在低温下的压力移动率.它随温度变化,表明温度和压力对Eu³⁺谱线作用不是独立无关的.按晶体场理论简化方法推导了能级的晶体场参数表达式,并按实验数据拟合出在不同低温下晶体场参数随压力的移     

Spin and temperature dependence of the magnetic hyperfine field of Cd in the rare earth-aluminum Lavesphase compounds RAl2

Perturbed angular correlation spectroscopy has been used to investigate the combined magnetic and electric hyperfine interaction of the probe nucleus ¹¹¹Cd in ferromagnetically ordered rare earth (R)-dialuminides RAl₂ as a function of temperature for the rare earth constituents R=Pr, Nd, Sm, Eu, Tb, Dy, Ho and Er. In compounds with two magnetically non-equivalent Al sites (R=Sm, Tb, Ho, Er), the magnetic hyperfine field was found to be strongly anisotropic. This anisotropy is much greater than the anisotropic dipolar fields, suggesting a contribution of the anisotropic 4f-electron density to magnetic hyperfine field at the closed-shell probe nucleus. The spin dependence of the magnetic hyperfine field reflects a decrease of the effective exchange parameter of the indirect coupling with increasing R atomic number. For the compounds with the R constituents R=Pr, Nd, Tb, Dy and Ho the parameters B₄, B₆ of the interaction of the crystal field interaction have been determined from the temperature dependence of the magnetic hyperfine field. The ¹¹¹Cd PAC spectrum of EuAl₂ at 9 K confirms the antiferromagnetic structure of this compound.     

Ga and Pt NMR study of UPtGa5

^69,71Ga and ¹⁹⁵Pt NMR/NQR measurements have been carried out for the 5f-antiferromagnet, UPtGa₅. From a NMR study using a single crystal sample, Knight shift measurements are reported for two different Ga sites and for Pt. The principal axes of the electrical field gradient tensor at both Ga sites have been determined and the values of the splitting parameter ν_Q and the asymmetry parameter η have been evaluated. The hyperfine coupling constants with the external field along various directions are also reported for the two Ga sites and Pt.     

EPR and optical absorption study of Cr-doped tetramethyl ammonium cadmium chloride single crystals

EPR study of Cr³⁺-doped tetramethyl cadmium chloride (TMCC) single crystals is carried out at room temperature. The crystal field and spin-Hamiltonian parameters are evaluated from the resonance line positions of different lines observed in the EPR spectra. The g and D parameter values are found to be g=1.9741±0.0002 and D=553±2×10⁻⁴ cm⁻¹, respectively. EPR data indicate that the site symmetry of Cr³⁺ ion in the crystal is distorted octahedron. Cr³⁺ ions enter the lattice substitutionally replacing Cd²⁺ sites and bind to the neighboring extra Cd vacancies necessary for charge compensation. The optical absorption spectra are measured in 195–925 nm wavelength range at room temperature. From optical study the energy values of different orbital levels are estimated. Further, the bonding parameters are obtained by correlating optical and EPR data and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are obtained to be B=722, C=2845, Dq=2043 cm⁻¹, h=1.015 and k=0.21.     

Temperature dependence of spin-hamiltonian parameters for chromium doped rutile

The temperature dependence of the spin-Hamiltonian parameters for substitutional Cr³⁺-ions in single crystal rutile (TiO₂) has been studied. The measurements were performed at about 9·2 GHz and 35 GHz on a fine powder of single crystalline Cr-TiO₂ for three temperatures, 95, 200, and 295°K. It was found that the spin-Hamiltonian parameter D diminishes with decreasing temperature in the temperature interval studied. The behaviour of g and E is more complex. A tentative extrapolation of the data towards 0°K has been made.