Calculations of the Overtone Transitions Of Sh− Pairs In KCl

In this work all vibration transitions up to the second overtone of pair SH^? molecules in KCl were calculated. The interaction of the identical molecules, which are characterized by “exact” resonance (equal pairs “SH^?—”SH^?, n = 32,33,34,36) were researched. The unequal molecular ions—“inexact” interaction (unequal pairs, “SH^?—^kSH^?, n≠ k, n, k = 32,33,34,36) were also considered. In both cases the problem was to find the eigenvalues of the matrix of dipole—dipole interaction that conforms to the solution of a secular equation. The elements of the dipole—dipole matrix were calculated in terms of the mechanical anharmonicity. It was supposed that the function of the dipole moment has linear dependence on the vibrational coordinate. The conditions of “exact” resonance and the conditions of “inexact” resonance diverged considerably. In the case of the “exact” resonance we used the orthogonal transformation of the dipole-dipole matrix and obtained a precise solution. In case of the “inexact” resonance we used the method of successive diagonalization. The intensities of the pair lines were calculated as well.     

Vibrational fluorescence of CN− centers in KCl by electronic excitation of neighbouring Tl+ centers

Abstract

Infrared emission from higher vibrational states of CN^? in KCl has been achieved by optically exciting nearby Tl⁺ ions with an excimer laser. The electronic vibrational energy transfer, already known from F_H(CN^?) in alkali halides, leads to population of vibrational states up to at least the tenth level.     

Simulating Suppression Effects in Pulsed ENDOR, and the ‘Hole in the Middle’ of Mims and Davies ENDOR Spectra

All pulsed electron-nuclear double resonance (ENDOR) techniques, and in particular the Mims and Davies sequences, suffer from detectability biases (‘blindspots’) that are directly correlated to the size of the hyperfine interactions of coupled nuclei. Our efforts at ENDOR ‘crystallography’ and ‘mechanism determination’ with these techniques have led our group to refine our simulations of pulsed ENDOR spectra to take into account these biases, and we here describe the process and illustrate it with several examples. We first focus on an issue whose major significance is not widely appreciated, the ‘hole in the middle’ of pulsed ENDOR spectra caused by the n = 0 suppression hole in Mims ENDOR and by the analogous A → 0 suppression in Davies ENDOR for I = ½ and for ²H (I = 1). We then discuss the general treatment of suppression effects for I = 1, illustrating it with a treatment of Mims suppression for ¹⁴N.     

ENDOR amplitudes of triplet state molecules: II. Orientational dependence of the νp frequency line and S-T0 mixing

The specific ENDOR line at the free Larmor frequency ν_p in the low temperature spectra of triplet state molecules is caused by degenerate NMR transitions within theM _s=0 zero-level (ZL) electron spin manifold. This ZL line was found to be orientationally dependent for the diradical complex Zn(3,6-di-tert-butyl-o-semiquinone)₂Zn(DBSQ)₂: the ZL line dominates the ENDOR spectrum if it is detected at the perpendicular canonical components of the EPR spectrum, and vanishes if the complex is oriented with its ZFSz-axis parallel to the direction of the magnetic field, i.e., if detected at the parallel canonical EPR components. This effect is shown to result from the interaction between nuclear spin substates of the S and T₀ manifolds, their levels being close to each other for the Zn(DBSQ)₂ complex. Such an interaction mixes the states and shifts energy levels. Consequently, it cancels the degeneracy of the nuclear substates within the ZL manifold and reduces the rate of nuclear flip-flop relaxation. This specific relaxation mechanism has been shown to substantially affect the amplitude of the ZL line (Doubinskii A.A., Lebedev Ya.S., Möbius K.: Appl. Magn. Reson.13, 439 (1997)). The nuclear flip-flop relaxation effect is expected to be orientationally dependent since the S-T_o separation depends upon the orientation of the diradical with respect to the external magnetic field.     

Dielectric properties of NaCl1−xBr and KCl1−xBrx mixed ionic solution

In the present paper a three-body potential model (TBPM) has been employed for the analysis of dielectric behaviour of NaCl-NaBr and and KCl-KBr mixed crystals with varying compositions. The physical properties like dielectric constants ( ₀ and ), optic mode frequencies ( _OLO and _TO), effective charge parameter (e _s ^* ), optic mode Grüneisen parameters and strain derivatives of ₀ and dielectric constants have been calculated. The results achieved in the present study are found in fairly good agreement with the available experimental data. The results obtained by previous investigators are also shown for the sake of comparison.     

Behaviour of F and Fz Centres Under Thermal Stimulation in KCl:Eu2☎ Irradiated with Ionizing and UV Radiation

The optical absorption (OA) of F and F_z, centres in beta-and UV-irradiated KCl: Eu^2? have been studied. The spectra measured at room temperature and during the subsequent heatings up to 600 K, were analyzed by a deconvolution procedure. The OA bands of the F and F_z centres are well described respectively by asymmetric and symmetric gaussiane with parameters that are linearly dependent on the temperature. The thermal stability of the F_z centres correlates with the low-temperature thermostimulated luminescence (TL) peaks. The stability of the F centres is determined at least by two processes. Part of the F centres is destroyed together with the F_z centres. The remaining ones are destroyed during further heating up to 470 K, correlating with the TL peak at 425 K (at heating rate of 0.1 K/s).     

The primary and secondary acceptors in bacterial photosynthesis III. Characterization of the quinone radicals Q A − ⋅ and Q B − ⋅ by EPR and ENDOR

Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) techniques were used to investigate the electronic structure of the primary (Q _A ^?? ) and secondary (Q _B ^?? ) ubiquinone electron acceptors in reaction centers (RCs) of the photosynthetic bacteriumRhodobacter sphaeroides. To reduce the EPR linewidth, the high-spin Fe²⁺ present in native RCs was replaced by diamagnetic Zn²⁺. Experiments were performed both on frozen solutions and single crystals at microwave frequencies of 9, 35 and 94 GHz. Differences in the EPR/ENDOR spectra were observed for Q _A ^?? and Q _B ^?? , which are attributed to different environments of the quinones in the RC. The differences exhibited themselves in: (i) the g-tensors, (ii) the¹⁷O and¹³C hyperfine coupling (hfc) constants of the quinones labeled at the carbonyl group, (iii) the¹H-hfcs of the quinone ring and (iv) the exchangeable protons hydrogen bonded to the carbonyl oxygens. From these results and from H/D exchange experiments, the following conclusions were drawn: both Q _A ^?? and Q _B ^?? have at least two hydrogen bonds of different strengths to the carbonyl oxygens. The hydrogen bonds for Q _A ^?? are stronger and more asymmetric than for Q _B ^?? . For Q _A ^?? the stronger bond (to O₄) was assigned to His(M219) and the weaker (to O₁) to Ala(M260). For Q _B ^?? the stronger bond (to O₄) was assigned to His(L190), with several weaker bonds (to O₁) to Ser(L223), Ile(224) and Gly(L225). From the temperature dependence of the hfcs of the exchangeable protons some dynamic properties of the RC were deduced. Hfcs with more distant nitrogens were observed by electron spin echo envelope modulation (ESEEM). For Q _A ^?? they were assigned to N_δ of His(M219) and to the peptide backbone nitrogen of Ala(M260) and for Q _B ^?? to N_δ of His(L190). These interactions indicate the extent of the electron wave function, which is important for the understanding of the electron transfer mechanism. Based on the magnetic resonance results, the function of the quinone acceptors in the reaction center is discussed.     

First-principles calculations and Bader analysis of oxygen-deficient induced magnetism in cubic BaTiO3−x and SrTiO3−x

The possibility of oxygen deficient induced magnetism in cubic BaTiO₃ (BTO) and SrTiO₃ (STO) perovskites is investigated by first-principles calculations, using the projector-augmented-wave method, within the generalised gradient approximation (GGA) and generalised gradient approximation with on-site effect (GGA + U), for the exchange correlation potential. For non-stoichiometric BaTiO_3?x and SrTiO_3?x, supercells were created in order to have two vacancy concentrations, i.e. x?=?0.125, 0.083. Spin charge distributions and magnetic moments associated with each ion, including local density of states projected in Bader atoms, were analysed by performing a full Bader charge analysis. Results show that oxygen vacancies could induce magnetism in BaTiO_3?x with x?=?0.125 and x?=?0.083 under GGA and GGA + U approximations. For SrTiO_3?x with x?=?0.125, ferromagnetism is induced with GGA, whereas with GGA + U the non-magnetic state is retained. On the other hand, with x?=?0.083, ferromagnetism is induced under GGA and GGA + U.     

Luminescence of Donor‐Acceptor Pairs in Compounds of Yttrium and Scandium Oxides

The luminescence spectra of Sc₂O₃, Y₂O₃, and Y₂GeO₅ ceramics and thin films exposed to laser and cathode excitation were investigated. The investigation of the properties of longwave luminescence bands in Sc₂O₃ with maxima at 2.65, 2.35, and 2.05 eV, in Y₂O₃ with maxima at 2.60, 2.35, and 2.10 eV, and also in Y₂GeO₅ with maxima at 2.55, 2.25, and 2.00 eV point to the fact that they are caused by radiative recombination of the excited donoracceptor pairs Sc³⁺ (or Y³⁺)O^2–.     

Observation and analysis of the Xe−I collisional-pair photoassociation spectrum

The interpretation of the photoassociation spectrum arising in collisions of Xe and I atoms is refined with allowance for new data concerning the interaction potential of Xe and I collisional pairs. Spectroscopic constants for the XeI(B) state are determined:R′ _e =3.264961 Å,D′ _e =33,289.05 cm^?1,w′ _e =113.867826 cm^?1, andw′ _e x′ _e =0.238304 cm^?1.     

FTIR stretching-mode measurements and calculations of equal and unequal pairs of SH− and SD− defects in KCI

Abstract

The fundamental stretching-mode absorption of molecular defects (ⁿSH^? or ⁿSD^?, where n = 32, 33, 34, 36) in KCI has four clear isotope-split lines. Due to the resonance interaction of the defects in pairs the absorption band of pair defects does not show the same isotope structure. We present here a theoretical approach for studying this phenomenon in KCI:SH:SD. The ions are assumed to preserve the [111] orientation of isolated defects and occupy the nearest neighbour anion sites. The results of the calculation show that the SH^? ions in the pair should have parallel or antiparallel directions to agree with the experimental spectrum.     

Laser oscillation by the F3− and F2− color centers in LiF crystal at room temperature

A stable, free-running LiF:F₃ ⁻ and LiF:F₂ ⁻ color center laser oscillation is achieved at room temperature by pumping with the 930-nm laser radiation. The LiF:F₃ ⁻ laser radiation has a peak at 1100 nm and shifts from the peak wavelength of the F₃ ⁻ luminescence band because of the absorption of the F₃ ⁻ luminescence by the F₂ ⁻ center, which co-exists with the F₃ ⁻ center. Received: 2 March 1999 / Revised version: 16 March 1999 / Published online: 12 May 1999     

An potential from analysis of ground and excited states of four-particle hypernuclei and Λp-scattering

A joint theoretical analysis is made of the binding energies of the ground and excited states of the four-particle hypernuclei and and the cross sections of low-energy p-scattering. We propose concrete variants of paired central spin-and charge-dependent n-potentials which are consistent with experiment.Translated from Izvestiya Vyssikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 62–65, May, 1982.     

Fluorene Based Ferric Complex as Colorimetric and Fluorometric Probe for Highly Selective Detection of CN− and S2− Anions

Journal of Fluorescence - A series of new chemosensor molecules bearing benzothiazole-, quinoline- and phthalazine-functionalized fluorene derivatives were synthesized and their complexation...     

Optical properties of (F2 +) H centers in NaCl:OH− crystals

Abstract

In this work we present new data on the formation and destruction of the laser active (F₂ ⁺)     

Connection Between Screw-Instability in Black Hole Magnetosphere and Pairs of High-Frequency Quasi-Periodic Oscillations

The correlation of screw-instability in black hole magnetosphere with pairs of high-frequency quasi-periodic oscillations (HFQPOs) is discussed in the coexistence of the Blandford-Znajek (BZ) and magnetic coupling (MC) processes. It turns out that screw-instability can result in HFQPOs. Such an HFQPO can be regarded as the transient process in an equivalent circuit with resistor and inductor in series (R-L circuit), and its period can be estimated by the relaxation time of this process. When the BZ process and the MC process coexist, the screwinstability can occur both in the BZ region and in the MC region, and the pairs of HFQPOs can be generated.Calculations show that such pairs of HFQPOs are likely to show frequencies in a 3:2 ratio. The frequencies of pairs of HFQPOs in our model scale inversely with the mass of central black hole, which is consistent with the observations.     

Phase transition and impedance spectroscopy analysis of Pb5(Cr1−xAlx)3F19 ceramics

Abstract

Analysis of the a.c. conductivity data of Pb₅Al₃F₁₉ within the complex permittivity formalism allowed, in a previous work, to show a new transition at 670 K corresponding most probably to the expected, but hitherto unobserved, transition from the paraelastic phase II to the paraelectric prototype phase I of Pb₅Al₃F₁₉. A new investigation of Pb₅(Cr_0.1Al_0.9)₃F₁₉ confirms this and allows us to complete the phase diagram of the Pb₅(Cr_1?x ;Al_x)3F₁₉ solid solution system for (0.80 ? x ? 1) in the high-temperature range. Ceramics with compositions corresponding to x = 0 and 0.5 were also characterized by this type of spectroscopy impedance method.