High temperature vibrational fluorescence of CN- ions in alkali halides

Infrared fluorescence from vibrational levels of matrix isolated CN^- ions has been studied in the temperature range of 300 K to 600 K. At 300 K the variation in the fluorescence lifetime from host to host is compatible with a multiphonon decay mechanism, but the measured temperature dependence does not agree with thermally induced multiphonon decay.     

Regularities in the luminescence spectra of solutions with molecular anion impurities

This article deals with the absorption, excitation and luminescence spectra of frozen aqueous solutions of the halide salts and acids with molecular anion impurities CN^-, SCN^-, SeCN^- and CNO^-. It is shown that the spectra at 4.2°K display vibronic structure which is explained by the interaction of electronic transition with intramolecular oscillations of the impurity. Conclusions are also deduced from the results of investigation of temperature dependence of the quantum emission efficiency and the Raman spectra of such systems.     

Investigation of the dynamical behaviour of the FH(CN−) centre in KCl with temperature dependent endor spectroscopy

Abstract

The temperature dependence of the electron nuclear double resonance (ENDOR) spectra of F_H(CN^?) centres in KCl was investigated in the temperature range between 10–220 K. At the lowest temperature of 10 K only one CN^? orientation with respect to the F centre electron is present, in which the nitrogen is thought to be nearer to the F-electron than the carbon. With the very small thermal activation energy of 2.9 meV the opposite orientation is occupied. The superhyperfine interactions of those first shell K nuclei nearest to CN^? and of the ¹³C interaction of the CN^? molecule are strongly temperature dependent between 10 and 60 K, following an exponential law with a thermal activation energy of 4.2 meV. It is assumed that a soft local mode involving those two nearest K nuclei and the CN^? is causing the strong temperature dependence. The shf interactions of ¹⁴N nuclei have not been seen, probably because of the dynamical effects.     

Observation of potassium hyperfine interactions in x-irradiated KH2AsO4 through the method of electron spin echo envelope modulation

Hyperfine interaction frequencies of ¹H and ³⁹K nuclei near the AsO^4-₄ radical in X-ray irradiated KH₂AsO₄ (KDA) have been observed through the method of electron spin echo envelope modulation (ESEEM). This method enabled us to record nuclear hyperfine interaction (ENDOR-like) spectra around the ferroelectric phase transition of KDA for the first time. The ESEEM spectrum of ³⁹K exhibits a clear change when passing the ferroelectric phase transition temperature, but that of close protons does not. The result for close protons is in agreement with the symmetry breaking of the AsO^4-₄ site as observed via the EPR spectrum [5]. Finally, at 4.2 K the hyperfine interaction parameters of a ³⁹K nucleus near the AsO^4-₄ unit could be determined through the ESEEM method.     

Synthesis,TGA and EPR studies of phase transitions in Cu2+ doped (NH4)4ThF8 and (NH4)3ThF7

The paper presents the EPR evidence for the occurrence of phase transitions in (NH₄)₄ThF₈ and (NH₄)₃ThF₇. In both cases the Cu²⁺ probe occupies a NH⁴⁺ site and predominantly experiences a dynamic coordination, either due to dynamic Jahn-Teller effect, or due to fluxional behaviour of surrounding (ThF₈)^4- units in (NH₄)₄ThF₈. It is proposed that the structural phase transition in this compound at 214 K is associated with the transition of the dynamic coordination of Cu^2- into a static one, probably due to freezing of motion of (ThF₈)^4- units below this temperature. In (NH₄)₃ThF₇ the dynamic features of the Cu²⁺ EPR spectrum are absent and characteristics of a local orthorhombic symmetry are seen down to 77 K. However, in the high temperature range a change from orthorhombic to axial symmetry is observed at 524 K, possibly due to a phase transition.     

Pairs of F centres and CN− molecules in KCl: An ENDOR analysis

Abstract

Pair defects consisting of F centres and CN^? molecules as substitutional impurity anions (F_H(CN^?) centres) exhibit a strong coupling between the F centres and the CN^? molecules. This leads to an optical pumping of the CN^? vibrations via the F centre absorption band. We performed an Electron Nuclear Double Resonance (ENDOR) investigation in order to analyse the microscopic structure of these aggregate centres. The CN^? molecule occupies a [110] nearest anion position with respect to the F centre in two dynamic dipole orientations even at low temperature.     

Phase transition of [(C6H5)3PCH3]+(TCNQ)-2 and electrical transport properties

The electrical conductivity at 10GHz, the dielectric constant, and the thermoelectric power (TEP) of [(C₆H₅)₃PCH₃]⁺(TCNQ)^-₂, from 230 up to 400 K, have been measured. This organic quasi-one-dimensional solid undergoes a first order phase transition at 314 K. At the transition the conductivity increases by a factor of 2.2 and the activation energy drops to 0.26 from 0.31 eV. At 314 K TEP decreases abruptly from -75 to -60μVK^-1 and remains almost constant for T > 314 K. The dielectric permeability ?₀ is constant and equal to 5 in the low temperature phase, increases abruptly by 7% at the transition, and then depends strongly on temperature in the high temperature phase. Results of the high temperature phase are interpreted in terms of a strongly correlated salt.     

Temperature evolution of the infrared spectrum of Ni(ClO4)2·6H2O

Temperature evolution of the infrared spectrum of the title compound confirms the phase transition temperatures 223, 311 and 355 K reported earlier and suggests a new phase transition at 180 K. From the spectral evidence, the transitions below the room temperature (～300 K) are attributed to tumbling motion of the metal aquo-complex, while those above the room temperature are attributed to reorientational motion of the water molecule. The space group in low temperature phases is suggested to be C²_s.     

High temperature Mössbauer studies of 57Fe: YSr2Cu3O7 related compounds containing oxyanions

Oxyanion substitutions at the copper sites can stabilize the Ba free phase YSr₂Cu₃O₇ and allow synthesis to occur under ambient conditions (P.R. Slater and C. Greaves, 1991; P.R. Slater et al., 1993). Here we report in situ ⁵⁷Fe Mössbauer spectroscopy experiments done in Y--Sr--Cu--O related oxides containing sulphate (SO₄ ^2-), phosphate (PO₄ ^3-) and borate (BO₃ ^3-), in the temperature range 300 K ? T ? 723 K. From the results obtained it has been possible to study the kinetics of oxygen loss, as well as the temperature dependence of the Fe species.     

Lumineszenz und Photochemie von Schwefelzentren in KCl und KBr

Interstitial hydrogen atoms are produced in alkali halides doped withSH ^–-molecules by UV-irradiation at low temperature. Tempering of the crystals leads to the formation of other sulphur centres which are investigated by optical luminescence and by electron spin resonance. The kinetics of these centres is discussed and models for several molecules are developped.     

Temperature dependence of EPR spectrum of Mn2+ doped in ammonium iodide single crystals

EPR of Mn²⁺ doped in ammonium iodide single crystal has been studied at X-band in the temperature range 573–577 K. The observed temperature dependence of line widths and spin Hamiltonian parameter b₂⁰ below room temperature is related to the structural transformations in the crystal. The coexistence of high temperature phase (NaCl) and low temperature phase (CsCl) is attributed to the large thermal hysteresis in line widths and b₂⁰. The dissociation of ion vacancy pairs occurs near 500 K and is reflected in the reversible change of an anisotropic EPR spectrum in an isotropic sextet near this temperature. The ion vacancy pair models for NaCl and CsCl phases are discussed along with the effects of thermal processing of the samples. Heating the crystals above 500 K leads to expulsion of Mn²⁺ impurity from the crystal.     

Raman scattering study of the low temperature phase of ammonium nitrate

Raman spectra of NH₄NO₃ and ND₄NO₃ have been recorded from room temperature down to 11K. A sluggish transition from phase IV to phase V was clearly observed but no evidence was found for another low temperature phase. Large splitting of the ν₃ mode indicates that the interionic interaction between NH⁺₄ and NO^-₃ is rather strong in both phases. A possible mechanism for the transition involving coupled modes is discussed.     

Paraelastic behavior of potassium cyanide

The low temperature Curie-type paraelastic behavior of low concentration anionic impurities dissolved in simple cubic alkali halide crystals has already been analysed for a number of cases. The CN⁻ radical in particular can substitute the halide ion in any concentration (up to 100% forming pure cyanide crystals), producing room temperature alkali halide-like crystals that above about 85% concentration show low temperature ferroelastic phases of crystallization. This paper presents the experimental evidence of room temperature paraelastic alignment exploring some analogies between elastic and magnetic (or electric) properties in the high concentration impurity range and above the phase transition (Curie) temperature.     

Effect of correlation on electronic properties of NiO: A study from dynamical mean field theory

In order to describe a typical strongly correlated insulator NiO at electronic level, we perform a first principles calculation for temperature effect on electronic properties of NiO using a many-body method merging local density approximation (LDA) with dynamical mean field theory, so called the LDA+DMFT scheme. Band gap and density of states (DOS) are in good agreement with available experimental data and theoretical calculations, and Ni d-e_g and d-t_2g components both exhibit insulating character. Calculated hybridization functions indicate that Ni d-e_g states strongly hybrid with O p states at T = 58 K, 116 K, 145 K, 232 K and 464 K. In order to compare with experimental angle-resolved photoemission spectrum (ARPES), we also calculate momentum-resolved electronic spectrum function, which is established that obvious electronic excitation mainly arises from Ni d-t_2g states at temperature T = 232 K, and the spectrum functions between −0.5 eV and 0.0 eV are almost symmetric about certain k points. Finally, we analyze the effect of temperature on electronic properties of NiO by carrying out LDA+DMFT calculations at T = 58 K, 116 K, 145 K, 232 K and 464 K, respectively. Results show that temperature mainly influences the valence states of spectrum function and hybridization function, in particular high-lying states close to Fermi level. Electronic excitation distributions and spectrum characters in electronic spectrum function are also discussed.     

Search for muon catalyzed d 3He-fusion

We report on the results of an experiment aimed at observing muon-catalyzed d ³He-fusion with a setup previously used for studies of the muon-catalyzed dd-fusion. The basic element of the setup is a high pressure ionization chamber operating as an active target. In this experiment the chamber was filled with an HD + ³He (5.6%) gas mixture at 13.2 bar pressure and 50 K temperature. These conditions were chosen as optimal for formation of the ³Heμd-molecules with a low level of background from the d-μ-d fusion. The chamber was exposed to the negative muon beam at PSI. During a 3-week data-taking period, 9.7 × 10⁸ muon stops have been selected. The analysis of the data was able to determine a new upper limit for the d ³He-fusion rate in the ³Heμd-molecule (λ_f≤ 6× 10⁴ s^-1), which is more than three orders of magnitude lower than the previously existed limit. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kerr effect of CN- molecules in KCl crystals

The electric field alignment of substitutional CN^- molecules in KCl crystals was studied by measurements of the field-induced optical birefringence (Kerr-effect). The electric field, temperature, wavelength and concentration dependence of the Kerr-effect and its pronounced anisotropy is found in quantitative agreement with a paraelectric alignment model for 〈111〉 oriented CN^- molecules, which have electronic absorption transitions hidden under the fundamental crystal absorption, and are characterized by an anisotropic polarizability of $\text{α}{}_6\text{? α}{}_{\mathrm{\perp }}\text{= 1.60}\text{A}\text{?}{}^3$.     

Superacid Catalyst SO42-/ZrO2-La2O3 Prepared by Ultrasonic Co-precipitation and Low Temperature Aging

低温陈化超声波共沉淀法制得SO₄^2-/ZrO^2-La₂O₃前驱体, 经H₂SO₄处理, 在不同温度下焙烧得到纳米晶催化剂SO₄^2-/ZrO^2-La₂O₃;用Hammett指示剂法测定其酸性. 用XRD、BET、TEM、IR和XPS对样品进行表征,其催化活性用醋酸和甘油的酯化反应进行了评价. 结果表明经超声波搅拌和低温(-15 ºC)陈化,650 ºC焙烧4 h得到的固体超强酸表现出较高催化活性.     

Synthetic metals based on tetramethyltetraselenafulvalene(TMTSF): Varied anisotropy in the low temperature (125K) structures of (TMTSF)2X,X=C104-, PF6-, and AsF6-.

The low temperature (125K) X-ray crystal structures of (TMTSF)₂X, X=C10₄^-, PF₆^-, and AsF₆^- reveal decreases in the intermolecular interand intrastack Se-Se contact distances upon cooling (298K to 125K) which are highly anisotropic and different from one salt to another. The changes in the interstack distances, which are normal to the stacking direction, are approximately twice those involving intrastack Se-Se interactions. These observations establish that the anisotropic structural changes which accompany decreased temperature are common to numerous (TMTSF)₂X radical cation conducting salts.     

Ferroelectric phase transition in PbHPO4 studied by IR-spectroscopy of internal modes

The spectrum of the internal modes in PbHPO₄ from 300 to 1100 cm^-1 is measured in reflection between 77 K and 370 K, and mode frequencies are determined by Kramers Kronig analysis. The spectrum is the ferroelectric phase is in agreement with space group Pc. The temperature dependence of the modes can be attributed to proton disorder. There is no indication of PO₄³-distortion in the phase transition and local ferroelectric order still exists in the paraelectric phase.