Том 121, № 4 (2016)

I present a critical overview of so-called “ab initio” DFT (density fuctional theory) based calculation schemes for the description of the electronic structure, energy spectrum, and optical response for strongly correlated 3d oxides, in particular, crystal-field and charge transfer transitions as compared with an “old” cluster model that does generalize crystal-field and ligand-field theory. As a most instructive illustration of validity of numerous calculation techniques I address the prototypical 3d insulator NiO predicted to be a metal in frames of a standard LDA (local density approximation) band theory.

The absorption spectra of LaF₃ crystals, both pure and doped with rare-earth fluorides (YF₃, CeF₃, NdF₃, PrF₃, SmF₃, EuF₃, GdF₃, TbF₃, DyF₃, HoF₃, ErF₃, TmF₃, YbF₃, and LuF₃) have been investigated. All these impurities can be separated into two groups with respect to the shape of the absorption spectra of irradiated crystals. The spectra of the crystals doped with Nd, Sm, Tm, and Yb exhibit, along with 200-nm hole band F₃^-, weak bands due to RE²⁺-anion vacancy centers. The spectra of LaF₃ crystals with Y, Ce, Pr, Gd, Tb, Dy, Ho, Er, and Lu impurities exhibit, along with the hole-center bands (F₃^- at 200 nm and V_kA at 320 nm), bands of comparable intensity, which can be attributed to RE³⁺–F centers. This conclusion is confirmed by preliminary quantum-chemical calculations and the estimation of the levels location in the energy-band diagram.

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.

The picosecond interband two-photon laser excitation of PbWO₄ crystals at a temperature of 10 K leads to electronic excitation energy accumulation, which results in almost 100% induced absorption in the 450–750 nm spectral range. The relaxation time of this induced absorption exceeds 100 min. The electronic excitation energy accumulated in the PbWO₄ crystal at T = 10 K excites the intrinsic luminescence with a decay time longer than 45 min. The decay kinetics and the spectra of the intrinsic luminescence of the PbWO₄ crystal at a temperature of 10 K were measured under two-photon and single-photon excitation. The luminescence under two-photon and single-photon excitation revealed a difference in the structure of the spectra.

Solid solutions CaLa_2–xNd_xGe₃O₁₀:Ho³⁺, Er³⁺ have been synthesized, their optical characteristics have been studied, and the dependences of the Stokes luminescence in the 0.9–3.0 µm region on the concentration of neodymium ions under 808 nm laser diode excitation have been determined. Based on analysis of the obtained dependences, the optimal composition of the phosphor with the maximum efficiency of the energy conversion is established.

The results of a complex analysis of the excitation mechanisms of the up conversion luminescence of Ho³⁺:LiYbF₄ (0.2 at %) crystal are presented. The spatial distribution of the upconversion luminescence intensity is studied by the photographs of longitudinal cross sections at different positions of the laser beam waist with respect to the sample. The surface power density of the pump laser diode radiation (0.755 W, λ = 933 nm) was changed by focusing the beam (similar to Z-scanning). The dependences of the longitudinal luminescence cross sections, as well as of the spectral and kinetic characteristics of Ho³⁺ and Yb³⁺ luminescence, on the position of the laser beam waist are determined. It is found that there exist two different mechanisms of the population of the energy levels of Ho³⁺ ions from which green and red luminescence occur, namely, cooperative sensitization of luminescence and absorption of induced photon groups (JETP Letters, 102 (5), 279 (2015)). It is shown that the contributions of these mechanisms vary both in time and over the crystal volume. All the observed spatial, spectral, and temporal specific features of the upconversion luminescence of Ho³⁺:LiYbF₄ (0.2 at %) crystal are qualitatively explained.

PrF₃ and LaF₃ nanoparticles were synthesized by the hydrothermal method. The size distribution of these nanoparticles in the colloidal solution produced was studied by photon correlation spectroscopy. The mean diameter of the nanoparticles was 42 ± 1 nm. During the study of the toxicity of the nanoparticles, the mixture of a colloidal solution of the nanoparticles with cells to be studied was irradiated by 30-mW continuous lasers at wavelengths of 532 and 473 nm. The concentration of salmonella cells in normal saline was 10⁶ cell/mL, while that of nanoparticles was 0.1 g/L. The cell survival percentage was 39, 34, and 20% for the irradiation times of 5, 10, and 15 min, respectively, at an optimal laser radiation power density of 0.4 W/cm at a wavelength of 532 nm. It was ascertained that LaF₃ nanoparticles do not possess the property of photoinduced toxicity and the apoptosing effect. Moreover, the property of photoinduced toxicity is not shared by microparticles, in contrast to nanoparticles.

This paper studies terahertz transmission spectra of silicon and erbium silicides which can be used to create uncooled bolometers for terahertz frequency domain.

A signal related to the spin level crossing in a zero magnetic field—the Hanle effect—has been registered for the first time in the EPR spectrum. It has been shown that, in the general case, the shape of the signal is determined by two qualitatively different mechanisms: (i) the interference of unsteady-state contributions to the dynamics of atomic coherences (electric or magnetic quantum transition moments with certain phases) with close frequencies (“beats at a zero frequency”) and (ii) the summation of resonant signals determined by the steady-state dynamics of the same atomic coherences. The relaxation time of spin coherences has been determined for the EPR transition of Tm³⁺ ions in synthetic forsterite.

Data on the influence of deuteration of organic molecules and/or solvent on their fluorescence quantum yield are summarized. It is demonstrated that the effect of deuteration is normal, i.e., deuteration increases the fluorescence quantum yield due to decrease in the internal conversion probability, for organic molecules exhibiting fluorescence in the red region of spectrum, in which the internal conversion competes with the emission of fluorescence. In the case in which the probability of internal conversion is low, i.e., energy of level S₁ ≥ 16000–20000 cm^–1, the intersystem crossing probability from the S₁ state to the set of triplet levels depends on the relative position of S₁ and the nearest triplet level. In so doing, the effect of deuteration can be either normal or anomalous, depending on whether the resonance between the S₁ level and the level nearest to it, the T_n level, improves or deteriorates when these levels shift as a result of deuteration. In dilute vapors, cooled supersonic jets, and crystalline matrices, including Shpolskii matrices, the effect of deuteration at helium temperatures depends on exact resonance between the interacting levels. In the case of dilute vapors and cooled jets, the effect also depends on the vibronic level being excited. Deuteration of OH and NH groups, as a rule, slows proton transfer in the S₁ state of the molecule that occurs with their involvement, leading to normal effect of deuteration.

A mechanism is suggested for the effect of oxygen on spectral sensitization of AgBrI microcrystals (MCs) with anionic dye adsorbed on the surface, which adequately describes the changes of both luminescent and spectral-sensitometric properties of this system. It is shown that the effect of oxygen on the spectral sensitization of AgBrI MC with anionic dye cannot be explained only by desensitization of the AgBrI MC sensitivity as has been suggested in the literature, but rather its effect on the spectral sensitization of AgBrI MC was not so unambiguous. In the framework of the suggested mechanism such ambiguity is due to the fact that the Ag⁺ and Ag₂⁺ silver centers that participate in the generation recombination processes and are different in structure, interact on the surface of the AgBrI MC with different aggregate forms of the dye, which are in turn differently affected by oxygen. Understanding physicochemical processes occurring in the considered system allows using the obtained results in holographic and spectrozonal photographic materials, gas-phase sensors, and in solar-energy systems.

The excitation of photon echo by noise pulses that are formed by modulation of the carrying frequency with Gauss noise is modeled. The modeling is based on optical Bloch equations the solution of which for noise pulse realizations is constructed by their stepwise approximation. In terms of the formalism of state transfer matrices, the two- and three-pulse excitation modes are analyzed. The complex envelopes of the primary and stimulated echo responses are determined. In the linear (low-level-signal) mode, the shape of the two-pulse echo corresponds to that of the time delayed and inverted noise pulse. The boundary of the linear mode, upon exceeding of which distortions of the shape of the noise pulse become noticeable, is determined. The shape of the stimulated (three-pulse) echo in the linear mode corresponds to that of the autocorrelation function of the noise pulse realization. Upon passage beyond the boundary of the linear mode, the shape of the three-pulse echo corresponds either to the cross-correlation function of distorted noise pulses (with different intensities) or to the autocorrelation function of distorted pulses (with the same intensities). The modeled photon echo excitation modes can be used in photon echo processors to process signals in the light range.

Surface waves that propagate along the interface between an isotropic linear or nonlinear (of the Kerr type) dielectric and a topological insulator have been studied theoretically. A dispersion relation for surface waves, which are represented by superpositions of TE and TM waves, has been obtained. This hybridization occurs because, upon passage through the interface, the polarization of a surface wave changes, which is caused by an induced surface current (which is transverse to the electric field vector of the wave). The surface current of this kind is characteristic of topological insulators. Expressions for the energy flux transferred by a surface wave have been given.