High pressure spectroscopy of chromium doped LiTaO3 crystals

Abstract

The effect of pressure on the luminescence spectrum of the weak field system Cr³⁺ : LiTaO₃ is presented. By using pressure to induce a low to high crystal field strength transition, we demonstrate the ability of pressure to identify distinct dopant bonding environments in luminescent materials.     

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     

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.     

GdOBr∶Eu晶场参数与自由离子参数的高压研究

在GdoBr∶Eu的常压和高压荧光谱实验数据基础上，对晶场能级及其重心进行了拟合计算，得到了晶场参数和自由离子参数（Slater参数和自旋 轨道耦合参数）在高压下的变化情况．计算结果表明，随压力增大，晶场参数B⁴₀，B⁶₀增大，B⁶₄减小，B²₀，B⁴₄的变化有些起伏．晶场强度在8GPa以 关键词：     

Effect of pressure on fluorescence of Nd3+ in LaCl3

Abstract

Fluorescence from Nd³⁺ in LaCl₃ is measured at 100 K under pressures up to about 10 GPa. The observed variations of the energy levels are used for the evaluation of crystal field parameters. The pressure-dependence of these parameters is compared with the previous results on Pr³⁺ in LaCl₃.     

Influence of the interconfigurational interaction on the crystal field of Ln3+ ions

A theory of the crystal field for Ln³⁺ ions is proposed which takes account of the difference in the effect of excited configurations on high-lying and low-lying multiplets. The effective-operator method in third-order perturbation theory is used to obtain the Hamiltonian of the crystal field, which in addition to the usual terms contains energy-dependent operators. Their role is discussed in detail. For the new operators we have obtained convenient expressions which make it possible for the first time to determine the parameters of an odd crystal field on the basis of an analysis of the structure of the energy spectrum. Theory is compared with experiment for the laser crystals Y₃Al₅O₁₂:Tm³⁺ and LiYF₄:Pr³⁺. Taking the new terms of the crystal-field Hamiltonian into account produces an additional shift of individual levels within the limits from −40 cm⁻¹ to 40 cm⁻¹ and makes it possible in a number of cases not only to substantially reduce the value of the standard deviation, but also to obtain the correct arrangement of levels. Zh. éksp. Teor. Fiz. 116, 2087–2102 (December 1999)     

Luminescence of Cs2NaScCl6:Pr3+: Effects of Changing the Elpasolite Lattice Parameter

Abstract

The luminescence spectrum of Cs₂NaScCl₆:Pr³⁺ (0.1 at.%) has been recorded at temperatures down to 10 K and assigned between 20,800 and 9900 cm^?1. Twenty‐three energy levels of the 4f² configuration Pr³⁺ ion were located and then fitted by the conventional 4f² crystal field calculation, as well as by a configuration interaction assisted crystal field (CIACF) calculation. The latter gave a much better fit. A comparison of the fit for Cs₂NaScCl₆:Pr³⁺ with fits upon the same set of energy levels in Cs₂NaYCl₆:Pr³⁺ and Cs₂NaPrCl₆, where the fifth nearest neighbor of Pr³⁺ is changed and the lattice parameter increases along this series, shows a decrease in the magnitudes of the crystal field parameters, which were also semiquantitatively simulated. Several facets of the emission spectra are interesting, including the observation of weak progressions in the totally symmetric Pr–Cl stretching vibration and the occurrences of the resonance of electronic and vibronic states. The spectra of Cs₂NaScCl₆:Pr³⁺ (1 at.%) differ considerably from those of the more dilute system and show that other species are formed rather than a complete substitution of the Sc³⁺ sites by Pr³⁺.     

An investigation on the magneto-optic properties of terbium gallium garnet under high magnetic field

The superexchange interaction on a magnetic ion may be represented by an effective field H_m = $\lambda$M in some paramagnetic materials, here λ is the coefficient of effective field and M = $\chi$H_e with $\chi$ being the magnetic susceptibility and H_e being the applied field. The variation of the equivalent $\lambda_{\chi}$with the dynamic applied field is given and the crystal field-splitting levels of the excited configuration 4f⁷5d¹ of the Tb³⁺ ion are calculated in the Tb₃Ga₅O₁₂. By means of the effective field H_m and the applied field H_e, the Faraday rotation of Tb₃Ga₅O₁₂ at 6 K and 41 K, under the high magnetic field and at 0.63 μm wavelength, are presented. Our calculated results are in agreement with the experimental data.     

Calculations of physical properties of pure and doped crystals: Ab initio and semi-empirical methods in application to YAlO3:Ce and TiO2

In this paper we demonstrate that two independent methods of calculations (DFT based ab initio and semi-empirical crystal field theory) can be used to form a complementary picture of the optical and electronic properties of the doped host and impurity ion. The crystals considered in the present paper are: (i) YAlO₃:Ce³⁺ and (ii) two dominant phases of TiO₂—rutile and anatase. As an example, detailed calculations of the band structure and crystal field energy level scheme of YAlO₃:Ce³⁺ are reported. From the analysis of the band structure and density of states, the character of the YAlO₃ energetic bands and positions of the Ce impurity energy levels were established. It was also shown how the ab initio methods can be used for calculations of the structural properties of solids under elevated pressure. Taking the two dominant phases of TiO₂ as an example, it was demonstrated how the elastic properties can be extracted from the calculated unit cell’s volume at different pressures. Particular attention was paid to the microscopic effects of crystal field, which were evidenced by the pressure-induced changes of the structure and shape of distribution of the Ti 3d electrons density of states. It was demonstrated how the difference in crystal structure of the anatase and rutile phases leads to remarkable difference in microscopic crystal field effects, which was explained by different Ti-O distances in both phases. In addition, the pressure dependence of the band gaps for anatase and rutile was investigated. It was shown that the hydrostatic pressure leads to the band gap narrowing in anatase and band gap widening in rutile, with pressure coefficients +0.00681 eV/GPa for rutile and −0.0088 eV/GPa for anatase.     

Forthcoming events 2001

Abstract

The magneto-optical spectra of the R₁ and R₂ lines of Cr³⁺ ions in alexandrite have been measured under hydrostatic pressures and magnetic fields up to 6 GPa and 15 T, respectively. The spins of the excited states, ²E, have the Heisenberg-type characters at atmospheric pressure, though the g-values are anisotropic with the values between 1.3 and 2.0. The g-values for the direction parallel to the α-axis remain unchanged with increasing pressure, while for the directions normal to the α-axis they are reduced appreciably. The fine structure parameters of spins in the ground state, ⁴A₂, exhibit quite a similar behavior. The R₁-R₂ splitting is reduced also by pressure. These properties are the evidences that the spins of the ²E states become of the king-type under pressures above about 15 GPa. The mechanism of such the change of spin character is discussed quantitatively on the basis of a crystal field model.     

Structural, spectroscopic and crystal field analyses of Ni2+ and?Co2+ doped Zn2SiO4 powders

In this paper we presented structural and spectroscopic study of zinc silicate powder samples doped with divalent nickel and cobalt ions. Results of the Rietveld structural refinement, combined with optical spectroscopic study and theoretical crystal field calculations, are presented and discussed. X-ray diffraction studies were performed to establish reliable structure of the doped samples; in this way the interionic distances and chemical bond angles in Zn₂SiO₄:Co²⁺ and Zn₂SiO₄:Ni²⁺ were calculated and are reported for the first time. The room temperature reflection spectra of the prepared samples were measured in a spectral region from 4000 to 50000 cm^?1. The exchange charge model of crystal field has been applied to analyze the experimental spectra and assign all observed details in the spectra to the corresponding electronic transitions between the Co²⁺ and Ni²⁺ crystal field energy levels. The only input information for the model calculation was the experimentally obtained structural data, which were used for the calculations of the crystal field parameters with subsequent diagonalization of the crystal field Hamiltonian for both ions. Agreement between the calculated and experimentally detected energy levels of impurity ions was good. On the basis of the crystallographic and crystal field studies it was established that there exists a systematic trend of preferential occupation of one out of two possible crystallographic sites (namely, Zn2) for both impurity ions.     

The determination of crystal field levels in the intermetallic compound HoRh by inelastic neutron scattering

Inelastic neutron time of flight measurements have been carried out on the intermetallic compound HoRh at different temperatures. Well resolved transitions between crystal field levels were observed at 4.0 and 9.7 meV. The complete crystal field level scheme was deduced and the crystal field parameters were found to be A₄⁰ 〈r⁴〉 = ?10.98 meV and A₆⁰ 〈r⁶〉 = ?1.59 meV. These values deviate considerably from point charge estimates.     

基质发光晶体Na5Eu(MoO4)4在高压下的光谱与晶体场参数

对白钨矿型化学计量的基质发光晶体四钼酸铕钠Na₅Eu(MoO₄)₄在室温下的高压光谱用金刚石对顶砧高压显微光谱系统进行了研究。确定了Eu³⁺各发射谱线的压力红移率。按晶场理论简化方法推导了能级的晶场参数表达式,并按实验数据拟会出晶场参数随压力的移动率。还将上述结果与掺杂发光材料YVO₄:Eu的高压光谱结果作了对比。 关键词：     

Pressure induced effects in forsixrite monitored by ESR

Summary

Chromium doped single crystals of Forsterite where investigated directly under the influence of uniaxial pressure in situ by ESR. The two Cr³⁺ centres M₁ and M₂ exhibit distinct response to the action of pressure on the crystal as a whole. The pressure effects are manifested in remarkable changes of the line width of the fine structure transitions. Uniaxial pressure in the MPa range induces nearly symmetrical distribution of distortions of the coordination polyhedra of the Cr³⁺ centres accompanied by reorientation effects.     

Crystal field analysis of energy level structure of the Cr2O3 antiferromagnet

A detailed analysis of the energy level structure of the six-fold coordinated Cr³⁺ ion in the chromium oxide Cr₂O₃ is performed using the exchange charge model of the crystal field theory. Parameters of the crystal field acting on the Cr³⁺ optical electrons are calculated from the crystal structure data for the [CrO₆]⁹⁻ impurity center. The energy levels obtained are compared with the experimental absorption spectra for the considered crystal; a good agreement with experimental data is demonstrated. One possible explanation for the ultraviolet p₁ absorption band is proposed based on the results of crystal field calculations.     

Pressure-induced closure of the jahn-teller distortion in Rb2CuCl4(H2O)2

This work investigates the pressure-induced variation of the local structure around Cu²⁺ as well as the crystal structure in Rb₂CuCl₄(H₂O)₂ through XAS and XRD techniques. The application of pressure induces a structural change in the Jahn-Teller (JT) [Formula: See Text] complex from axially elongated to compressed. This change leads to the closing of the 2D JT distortion related to the four in-plane Cl^? ligands, which are responsible for the antiferrodistortive structure displayed by the crystal. It is shown that the presence of water ligands enhances a JT release. Their associated axial ligand-field favours the occurrence of such a local structural transition below the metallization pressure. The results are compared with recent pressure experiments on A₂CuCl₄ systems.     

Investigation of Nd2CuO4 crystal structure at high pressure by neutron diffraction

Abstract

The crystal structure of Nd₂CuO₄ has been studied by neutron diffraction at pressure up to 5 Gpa. The volume compressibility value was determined as 5·6·10^?3/Gpa. The decrease of positional parameter of neodymium at high pressure has been observed. This structural change is explained by pressure induced neodymium ions charge increase.     

The kinetics of solidification of Al-Si eutectic alloys under high pressure

Abstract

The kinetics of crystallization of eutectic alloys Al_100-xSi_x (χ=12, 18, 26 at.%) was investigated under pressures p=0.5, 2.5, 4.5 GPa. The values of supercooling and average grain size of silicon crystals were determined for alloys quenched from melt under different pressures with the cooling rate 10³ K/s. The data obtained were used to evaluate quantitatively the pressure dependences of surface tension (between melt and crystal) and activation energy of crystal growth which, in turn, have made it possible to determine the relative change of nucleation frequency and of the rate of crystal growth with pressure.

The possibility is shown, based on the investigation of mechanical properties of the samples obtained under high pressure, for improving the strength and the plasticity of A1-Si alloys by means of high pressure-high temperature treatment.     

Fundamental Concepts of Electron Spin Resonance Technique in the Determination of the Crystal Field Structure of O− 2 Ions in TiO2

Abstract

The basic principles of Electron Spin Resonance (ESR) as applicable in crystal field characterization of paramagnetic species has been outlined. Fundamental concepts of the precessional motion of electrons and their magnetic moments at resonance were developed. The theory of ESR based on the response of unpaired electron(s) as they undergo spin-spin or spin-lattice relaxation when subjected to strong external magnetic fields was examined. Ions of the O^? ₂ group adsorbed on TiO₂ were studied using a Varian Spectrometer. The resulting spectral diagrams obtained were used in calculating the g-factors which gave results for orthorhombic crystal symmetry for O^? ₂ ions in TiO₂.     

掺铒硅发光的晶场分裂

测量了掺铒硅的高分辨光致发光光谱，得到9条铒发光分裂谱线.利用群对称理论指出9条谱线来自Er³⁺中⁴I_13/2到⁴I_15/2光跃迁在T_d晶场下的分裂.Er³⁺的第一激发态⁴I_13/2最低能量的两个Stark能级为Γ₈，Γ₆(能量递增)，它们到基态⁴关键词：