EPR characterization of Mn impurity ions in PbWO4 single crystals

The electron paramagnetic resonance (EPR) properties of the Mn²⁺ ions in PbWO₄ single crystals grown by the Czochralski method have been investigated in the X-band microwave frequency, at T=20 K. The angular dependence of the EPR line positions obtained by rotating the magnetic field in the main crystallographic planes shows that the local symmetry at the Mn²⁺ impurity ions is tetragonal, strongly suggesting that the Mn²⁺ ions substitute for the Pb²⁺ lattice cations, without charge compensation. The resulting spin Hamiltonian parameters compare well with the corresponding values for the Mn²⁺ ions in other isomorphous tungstates. The observed strong angular variation of the EPR linewidth has been quantitatively described considering a random distribution of lattice strains.     

ENDOR and transferred hyperfine interaction of impurity rare-earth ions with nearest diamagnetic ions in crystals

The tetragonal Er³⁺ ion associated with the interstitial F^? ion along the [100] axis in CaF₂ is studied using ENDOR. The parameters of the transferred hyperfine interaction and of the nuclear Zeeman interaction of the surrounding fluorine ions are determined. Anomalously large values of the pseudo-nuclear Zeeman effect on the F^? nuclei are found. The theoretical analysis of these parameters is carried out in a frame of operator techniques in the theory of transferred hyperfine interactions. A number of useful relations for practical calculations of the values of the local field at ligand nuclei are reported.     

The origin of the isotropic EPR spectrum of a Jahn-Teller impurity in crystals

The motional narrowing processes and their contribution to the origine of the isotropic EPR spectrum of a cubic ²E — term in the cases of strong linear and both weak and strong second-order vibronic interaction, are investigated. It is shown that these relaxation processes are nonefficient at low temperature, and the isotropic spectrum is associated with the nearest exited vibronic singlet level.     

Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review

The results of observation and simulation of the superhyperfine (ligand hyperfine) structure (SHFS) of the electron paramagnetic resonance (EPR) spectra of rare-earth and uranium impurity ions in dielectric crystals have been systematized. The resolved SHFS of the EPR spectra of doped cubic crystals (with the fluorite and perovskite structures) has been observed for orientations of a constant magnetic field along the crystallographic axes. Most attention has been paid to tetragonal double fluorides LiRF₄ (R = Y, Lu, Tm), in which the SHFS of the EPR spectra has also been found for intermediate orientations of the magnetic field. For the LiYF₄: Nd³⁺ single crystal, the splitting of optical spectral lines due to the interaction of Nd³⁺ ions with nuclear magnetic moments of the nearest neighbor fluorine ions has been observed for the first time. The Van Vleck paramagnet LiTmF₄: U³⁺ is characterized by the SHFS with clearly distinguishable components due to the interaction of uranium ions both with nuclei of the fluorine ions and with enhanced magnetic moments of the thulium nuclei. The SHFS envelopes of the EPR spectra of Yb³⁺, Ce³⁺, Nd³⁺, and U³⁺ ions in LiYF₄ and LiLuF₄ crystals are well reproduced by numerical calculations based on the microscopic model using only three fitting parameters: the width of transitions between the electron-nuclear sublevels of the complex containing the paramagnetic ion and nuclei of the ligands and two constants of covalent bonding of the f electrons with 2s and 2p electrons of the nearest neighbor fluorine ions.     

Covalency and EPR hyperfine structure constant of Eu2+ in crystals

The covalent reduction of the EPR hyperfine constant of Eu²⁺ in different crystals is presented as esulting from the exchange polarization mechanism. Free-ion values of hyperfine constants of Eu²⁺ isotope are calculated.     

Dimer self-organization of impurity ytterbium ions in synthetic forsterite single crystals

Paramagnetic centers formed by impurity Yb³⁺ ions in synthetic forsterite (Mg₂SiO₄) grown by the Czochralski technique are studied by X-band CW and pulsed EPR spectroscopy. These centers are single ions substituting magnesium in two different crystallographic positions denoted М1 and М2, and dimer associates formed by two Yb³⁺ ions in nearby positions М1. It is established that there is a pronounced mechanism favoring self-organization of ytterbium ions in dimer associates during the crystal growth, and the mechanism of the spin–spin coupling between ytterbium ions in the associate has predominantly a dipole–dipole character, which makes it possible to control the energy of the spin–spin interaction by changing the orientation of the external magnetic field. The structural computer simulation of cluster ytterbium centers in forsterite crystals is carried out by the method of interatomic potentials using the GULP 4.0.1 code (General Utility Lattice Program). It is established that the formation of dimer associates in the form of a chain parallel to the crystallographic axis consisting of two ytterbium ions with a magnesium vacancy between them is the most energetically favorable for ytterbium ions substituting magnesium in the position М1.     

Hyperfine structure of submillimeter EPR spectra of non-Kramers lanthanide ions in crystals

The hyperfine structures of submillimeter EPR spectra of CsCdBr₃:Tm³⁺ and CaF₂:Dy²⁺ single crystals have been resolved and analyzed. The crystal field parameters and the magnetic hyperfine constants are obtained from fitting the envelopes of the simulated spectra to the measured signals. From the specific peculiarities of the hyperfine structure the energy of the interion interaction in the thulium dimers in CsCdBr₃ is determined. The isotopic shift of the crystal field splitting in energy patterns of dysprosium isotopes in CainF₂ is estimated.     

Luminescent spectroscopy and structure of centers of the impurity Eu ions in lead tungstate crystals

Spectral-luminescent properties of the lead tungstate crystals doped with the Eu³⁺ ions were investigated in a wide temperature range at different excitation and registration wavelengths. The spectra consist of both weak wide nonstructural bands of the matrix emission and narrow spectral lines caused by inner f-f electron transitions in the impurity Eu³⁺ ions. The analysis and interpretation of spectral lines observed in excitation and luminescence spectra have shown formation of at least two different types of luminescent centers on the basis of the Eu³⁺ ions in the PbWO₄ crystals. These two types of centers are considered to be caused by arrangement of the impurity Eu³⁺ ions in Pb sites as well as in W sites of host matrix. For both types of centers values of S² scalar crystal field strength, and crystal field parameters were estimated and local site symmetries were found.     

Concepts for the measurement of hyperfine structure in EPR spectroscopy

Continuous wave and pulsed EPR methods for the measurement of hyperfine interactions are reviewed.     

EPR and IR spectral studies on Mn ions in nickel maleate tetrahydrate single crystals

Electron paramagnetic resonance (EPR) studies have been carried out on Mn²⁺ ions doped in nickel maleate tetrahydrate single crystals in the temperature range 103-413 K on X-band frequency. The EPR spectrum at room temperature exhibits a group of five fine structure transitions each splits into six hyperfine components. Angular variation studies reveal the presence of a single site and it is found that Mn²⁺ ions enter the lattice substitutionally. From the observed EPR spectrum, the spin-Hamiltonian parameters have been evaluated. The variation of zero-field splitting parameter (D) with temperature is measured. The observed EPR spectra exhibit a large anisotropy in the widths of Mn²⁺ resonance lines. The widths of Mn²⁺ resonance lines increase with the Zeeman field intensity and these observations have been discussed in detail. The infrared spectrum exhibits bands characteristic of the carboxylic acid salts.     

Some peculiarities of spin-lattice relaxation of impurity rare-earth ions in crystals caused by the structure defects

The spin-lattice relaxation times for Nd³⁺ ions in yttrium-aluminum garnets (YAG) and for Yb³⁺ ions in CaF₂ in the low-temperature range have been measured. For the first system the temperature dependence of the relaxation rate is determined to a great extent by the method of sample preparation. For samples grow by the method of the horizontally oriented crystallization the dependence is described asT ₁ ^?1 =AT ⁿ ,n ? 4.7, which is an evidence of an influence of local structure disordering on the relaxation. The temperature dependence of the relaxation rate in CaF₂:Yb is also “anomalous”:T ₁ ^?1 =AT ^3.3. The results are compared with the previous data on the relaxation in similar systems, and with other cases of observation of “anomalous” temperature dependences. Different manifestations of the local crystal defects in spin-lattice relaxation are discussed.     

钕离子同位素移位和超精细结构光谱

原子光谱中,同位素移位和超精细结构光谱是少数几个能够将原子物理和原子核物理这两个不同的物理分支联系起来的课题之一.利用共线快离子束-激光光谱学方法测量了单电荷态钕离子4f45d6G3/2→(26041)°5/2跃迁(波长577.21 nm)的共振光谱,得到了所有7个稳定同位素(A=142～146,148,150)之间的能量移位和2个奇同位素(A=143,145)的超精细结构光谱.     

Anisotropic dynamic response of pentacene single crystals

We have investigated the polarization and momentum dependence of singlet excitons in pentacene molecular crystals using inelastic electron scattering. Our results demonstrate that both the direction as well as the absolute value of the momentum are decisive for the spectral intensity of these excitons. Possible implications of this observation for a microscopic understanding of excitons in organic molecular crystals are discussed.