Temperature dependence of the emission spectra of p-benzoquinone in a p-dichlorobenzene matrix

Emission and excitation spectra of p-benzoquinone have been measured in a partially translucent p-dichlorobenzene host matrix at different temperatures from 77 up to 323 K. Successive occurrence of the T₁(n,π^?) and T₂(n,π^?) phosphorescence and S₁(n,π^?) fluorescence has been observed for p-benzoquinone upon increasing temperature. The S₁–T₂ and T₂–T₁ energy separations determined from the temperature dependence of the emission intensities agreed well with those obtained from the locations of the T₁ and T₂ phosphorescence and S₁ fluorescence origins. Occurrence of the emission from S₁ and T₂ is brought by the thermal population from the T₁ state. The symmetries of the T₁ and T₂ states were determined to be B_1g and A_u, respectively, based on the spectral data.     

Observation of the distorted form of Pd-porphin in single site spectra at low temperatures

Highly resolved phosphorescence and excitation of phosphorescence spectra for palladium porphin (PdP) in polycrystalline Shpol'skii matrices at liquid helium temperatures were recorded. Two non-interactive forms of PdP in the ground state have been identified. The energy splitting between the two forms amount up to 78 cm⁻¹ for PdP in an n-octane at 4.2 K. The short-wavelength spectral form is attributed to the structure, where the central Pd(II) ion is in plane of the porphyrin macrocycle, while the long-wavelength form is associated with the nonplanar saddle-type conformation of the PdP. The frequencies of the normal vibrations in the ground electronic state have been measured separately for both forms and the differences in the normal modes of two macrocycle conformations are discussed. The set of temperature activated bands in phosphorescence spectra were found. Analysis of phosphorescence spectra at elevated temperatures and excitation of phosphorescence spectra under direct excitation in the S₀→T₁ channel make possible the value of zero-field splitting of quasi-degenerate T_1,2 state for two forms to be determined. The splitting value in n-octane matrix amount to 40 and 57 cm⁻¹ for planar and nonplanar conformations of PdP, respectively.     

Solvent and temperature dependence of the phosphorescence decay time of hexacyanochromate (III)

The temperature dependence of the ²E_g - ⁴A_2g phosphorescence of tetrabutylammonium hexacyanochromate (III) dissolved in various solvents has been measured within the liquid range of these solvents. In this limited temperature range, the reciprocal decay times obey Arrhenius relationship. From the absence of a solvent isotope effect, in ethanol and methanol and their monodeuterated analogues it is concluded that hydrogen bonds between the solvent and the complex ion do not provide promoting or accepting modes for the radiationless deactivation. The room temperature decay times have been found to correlate with the solvatochromic shift of the ⁴A_2g ? ⁴T_2g absorption bands and with Dimroth's E_T parameter. According to the selection rules for non-radiative decay a combination of CN stretching with either a Cr-C-N bending or a Cr-C stretching vibration is postulated as the promoting mode.     

London penetration depth and coherence peak in ammonia-intercalated fulleride superconductors

The compound (NH₃)_xNaRb₂C₆₀ (x ～ 1.6) has been studied by¹H nuclear magnetic resonance. The proton line shows no shift at any temperature, while lineshape analysis of the low-temperature (30 K) spectra reveals the presence of a Knight shift interaction of pure anisotropic nature, whose amplitude has been estimated. Relaxation measurements show a single-exponential recovery of the magnetization at all investigated temperatures and fields. A Korringa behavior is observed below 65 K and a clear Hebel-Slichter coherence peak is detected just below T_c. The London penetration depth can be estimated from the line broadening observed below T_c, which yields λ ≈ 825 nm.     

Mössbauer study of the transition metal phosphorus trichalcogenide FePS3 and spin glass Mn0.5Fe0.5PS3

The transition metal phosphorus trichalcogenides MnPS₃ and the FePS₃ are CdCl₂ type layered compounds, where the transition metal ions form a hexagonal lattice. While these compounds order anti-ferromagnetically at low temperature, the magnetic structures are different. We have reported that these mixtures Mn_0.5Fe_0.5PS₃ is a spin glass with a glass transition temperature T _g=33.7 K. Then, in this work, we report that the results of the temperature variation of the ⁵⁷Fe Mössbauer spectra of FePS₃ and Mn_0.5Fe_0.5PS₃, in detail. In the anti-ferromagnetic state of FePS₃, the hyperfine magnetic field H _int increases with decreasing temperature and the Isomer shift I. S. increases slightly with decreasing temperature. However in Mn_0.5Fe_0.5PS₃, the two broadened peaks are observed and the two peaks became a single peak with decreasing temperature at about 50.0 K, which is higher than T _g=33.7 K. In the spin glass Mn_0.5Fe_0.5PS₃, the Mössbauer spectra suggest that the magnetic interactions exist far above T _g.     

Multifrequency EPR of four triarylmethyl radicals

Continuous-wave spectra at W-band of four triarylmethyl (trityl) radicals at 100 K in 1∶1 water-glycerol exhibit rhombic electron paramagnetic resonance spectra. The rigid-lattice line widths at W-band are only 3 to 5 times larger than at X-band or S-band, and fluid-solution line widths are much narrower than those for rigid lattice, which indicates that unresolved anisotropic nuclear hyperfine couplings make significant contributions to the rigid-lattice line widths. Spin-flip lines are observed in glassy-solution spectra at X-band and S-band, but not at W-band or 250 MHz. At 100 KT _m is dominated by spin diffusion of solvent protons and is independent of microwave frequency. Between about 130 and 170 K, 1/T _m for trityl-CH₃ is enhanced by rotation of the methyl groups at a rate comparable to inequivalences in the hyperfine interaction. Motional averaging of anisotropic interactions enhances spin echo dephasing between about 200 and 300 K. The temperature dependence of 1/T ₁ is similar for the four radicals and is consistent with assignment of the Raman process and a local mode as the dominant relaxation processes. The similarity inT ₁ values at W-band and X-band supports this assignment.     

Central peak in the strontium titanate crystal near the tetragonal-to-cubic phase transition

Raman spectra of the SrTiO3 crystal have been measured in wide temperature (22?C316 K) and frequency (2?C1020 cm^?1) ranges. It has been shown that a central peak appears in low-frequency Raman spectra at temperatures above 70 K. In the spectral geometry with polarization rotation near the temperature T _c = 106 K of the cubic-to-tetragonal phase transition, the central peak exhibits properties of the order-disorder phase transition. Such a behavior of the central peak has been explained by the interaction of the low-frequency soft mode E _g with the relaxation mode near T _c .     

Specific features of the central peak in the Raman spectra of a lithium niobate crystal

The low-frequency Raman scattering (RS) spectra of a LiNbO₃ ferroelectric crystal are studied in the temperature range 300–1423 K. The central peak characterizing the relaxation susceptibility of the crystal lattice is observed over the entire temperature range studied, including at temperatures much lower than the Curie temperature (T _c = 1470 K). Far from T _c, the characteristics of the central peak are shown to be unlike those expected in the framework of the standard approaches. (i) The central-peak width γ_R increases as the temperature increases to T ～ 1300 K, and the critical slowing down (γ_R ∝ T _c ? T) occurs only above this temperature. (ii) A central peak arises in the RS geometry where the scattering by “nonferroelectric” E phonons is allowed. The experimental results are interpreted with allowance for relaxation dynamics in local regions of the crystal lattice.     

Manifestation of nonplanarity effects and charge-transfer interactions in spectral and kinetic properties of triplet states of sterically strained octaethylporphyrins

Properties of the triplet states of octaethylporphyrins with the steric hindrance (free bases and Pd complexes) are studied by the methods of stationary and kinetic spectroscopy in the temperature range from 77 to 293 K. The mono-mesophenyl substitution results in a decrease in the quantum yield and shortening of the phosphorescence lifetime of Pd complexes by 250–3500 times in degassed toluene at 293 K. The phosphorescence quenching is caused by nonplanar dynamic conformations of the porphyrin macrocycle in the T ₁ state, which also lead to the appearance of new bands at λ～1000 nm in the T-T absorption spectra. As the number of meso-phenyls (Pd-octaetyltetraphenylporphyrin) increases, the quantum yield of phosphorescence further decreases (<10^?5) at 293 K, the lifetime of the T ₁ state shortens (<50 ns), and the efficiency of the singlet oxygen generation abruptly decreases (<0.01). The intense bathochromic emission of this compound at 705 nm with a lifetime of 1 ms at 77 K is assigned to the phosphorescence of a nonplanar conformation. Upon meso-orthonitrophenyl substitution, the quenching of phosphorescence of Pd complexes (by more than 10⁴ times at 293 K) is caused by direct nonadiabatic photoinduced electron transfer from the T ₁ state to the nearest charge-transfer state with the probability k _et ^T =(1.5–4.0)×10⁶ s^?1. The induced absorption of ortho-nitro derivatives in the region between 110 and 1400 nm is caused by mixing of pure ππ* states with charge-transfer states.     

Spectral manifestations of nonplanarity effects in Pd complexes of porphyrins

It is found on the basis of kinetic spectral studies in nonane, dodecane, and vitreous solutions at 77 K (phosphorescence spectra, polarized phosphorescence, decay kinetics, and phosphorescence excitation spectra) that symmetric and nonsymmetric Pd-porphyrins are characterized by the presence of two noninteracting spectrally different long-and short-wavelength forms in the ground state. The existence of the long-wavelength form is associated with the displacement of the central Pd ion from the macrocycle plane, which leads to the formation of the nonplanar “dome” conformation of the porphyrin ligand. In the case of a nonsymmetrically substituted Pd-tetramethyl-diethylporphyrin molecule, the nonplanar conformation of the π-conjugated macrocycle is characterized by the splitting of the triplet state into two components (T ₁ and T ₂, Δν=90 cm^?1 at 77 K). Both narrow components, which have the same decay, form a dual phosphorescence of the long-wavelength form of this compound, which is caused by efficient thermal exchange between T ₁ and T ₂ levels in the course of deactivation to the ground state.     

Phase transition study in α-Fe2WO6 compound by EPR

The temperature dependence of the EPR spectrum for the α-phase of iron tungstate has been investigated in the temperature range of 40–260 K. At temperatures betweenT ₁ ≈ 250 K andT ₂ ≈ 205 K where the antiferromagnetic phase transition occurs, a relatively narrow EPR line arising from the dominant iron(III) species has emerged, gaining intensity with the temperature increase. Its linewidth temperature evolution could be described by Huber equation, with T_N = 200 K, which is consistent with the peak seen in magnetic susceptibility measurements, while the correspondingg-factor shifts to higher fields reflecting the build-up of internal field emerging from increasing shortrange order in the spin system. At temperatures lower than T₂, a very broad and distorted EPR line with temperature dependentg-factor and linewidth has been observed reflecting the corresponding rise of the magnetic susceptibility below the antiferromagnetic phase transition, presumably arising from magnetic clusters embedded in the antiferromagnetic background.     

Effect of surface temperature on the sorption of hydrogen by Pd(111)

Temperature programmed desorption (TPD) subsequent to various hydrogen exposure conditions indicates the formation of chemisorption, solid solution, and hydride phases of hydrogen in the near surface region of Pd(111). Variation of the sample exposure temperature (T_e) between 80 and 300 K has a strong effect on the subsequent TPD spectra. At T_e = 80 K a single desorption peak, β, appears at 310 K. Coverage variation of the β peak is consistent with second-order recombinative desorption of chemisorbed hydrogen. For T_e between 90 and 140 K a slight enhancement of the β peak occurs and a new peak, α, appears initially near 170 K. It does not saturate, exhibits near-zeroth-order desorption kinetics, and is assigned to the decomposition of a near surface palladium hydride phase. Population of the α peak is thermally activated with a maximum at T_e ≈ 115 K. For T_e, greater than 140 K, α disappears while the total amount of absorbed hydrogen increases significantly. At these temperatures, the concentration of absorbed hydrogen decreases significantly if the sample is held in vacuo at T_e after completion of the hydrogen exposure. At all exposure temperatures there is also a broad desorption feature near 800 K which is enhanced by higher T_e and is associated with hydrogen in solid solution.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Thermal desorption of Ag from oxidized W

Thermal desorption spectra (TDS) of Ag condensates deposited at two substrate temperatures T_s = 300 K and T_s = 779 K have been obtained. A shift of the temperature T_m of the maximum of the desorption flux R_e was observed. It was established that the shift of the maximum depends on the value of the initial coverage σ₀. A significant difference was found to exist between TDS of silver condensates deposited on oxidized and clean W substrates due to differences in the mechanism of condensation. Silver condensates were deposited on oxidized W at different initial conditions (T_s, impingement rates R_i, etc.) but equal σ₀. The corresponding TDS were compared and a conclusion has been drawn that the shift of T_m is due to the different structure of Ag condensates. TDS of Ag condensates deposited at room temperature (T_s = 300 K) were interpreted using the method of Bauer et al. [J. Appl. Phys. 45 (1974) 5164: Surface Sci. 53 (1975) 87]. The dependence of the desorption flux R_e on the substrate temperature T_s and coverage σ was treated on the basis of the Polanyi-Wigner equation and some parameters of the condensation process were evaluated.     

Radiative properties of α-ZnAl2S4:V spinel type single crystals

The absorption and luminescent properties of α-ZnAI₂S₄:V spinel type crystals in the temperature range 10-300 K are investigated. The spectra are assigned to the electronic transitions of trivalent vanadium ions located in octahedral sites. It is shown that at low temperatures the three main components of the revealed IR luminescence spectra are caused by the ¹A_1g(¹G)→¹E_g(¹D), ¹T_2g(¹D), ³T_2g(³F)→³T_1g(³F), and ¹E_g(¹D)→³T_1g(³F) transitions. The observed dependencies of the emission components intensities on temperature are explained assuming that there is a phonon assisted tunnelling between ³T_2g(³F) and ¹E_g(¹D) states. On temperature rise, the ³T_2g(³F)→³T_1g(³F) vibronic transitions suppress other emission channels, which leads to the enhancement of the integral luminescence intensity and to the broadening of the spectrum centred at λ=1.4 μm.     

Magnetic and related properties of GdCu5.1In6.9

Magnetic measurements performed between 1.7 and 300K show that GdCu_5.1In_6.9 is an antiferromagnet below T _N = 13.4(1) K. At temperatures 17–300K the Curie-Weiss law is followed with p _eff = 7.57 μ _B and θ = -33.8K. Electrical resistivity measurements do not show any pronounced anomaly, but the resistivity is rather low with RRR ≈ 59. The EPR experiment shows that the resonance exists between 10 and 300 K. A temperature independent g-shift (Δg = -0.036(10)) and a Korringa.type linewidth broadening of 2.6 G/K was observed at temperatures higher than 55 K. The linewith increase found at high temperature well above T _N can suggest a significant amount of short. range order. ¹⁵⁵Gd Mössbauer effect examinations show that H _hf is perpendicular to the c-axis and therefore magnetic moments of Gd are located within the ab-plane.     

Pressure and temperature induced modification of luminescence from tetracene single crystals

Fluorescence spectra of crystalline tetracene have been recorded in the temperature range 120 to 300 K under hydrostatic pressure up to 600 MPa. From discontinuities in both emission spectra and spectral intensities it is concluded that two phase transitions occur. The room temperature phase is transformed to a low temperature phase/high pressure phase I at T^I_t (p = 0) = 182 K, the temperature coefficient being dT^I_t/dp = 0.395 K/MPa. The phase transition is induced by a decrease of the specific volume under pressure and/or upon cooling. Lack of a significant shift of the origin of the fluorescence band near T^I_t at constant pressure is an artifact resulting from the neglect of reabsorption effects. The Stokes shift is 260 cm^-1, independent of temperature and crystal modification. In accord with previous Raman data a second phase transition occurs at T^II_t (p) = 143 K, the pressure shift being dT^II_t/dp = 0.088 K/MPa.In addition, the shift of the triplet energy as a function of pressure as well as the pressure-dependence of the rate constants governing fission of a singlet exciton into a pair of triplets is discussed utilizing their magnetic field dependences.     

Etude par spectrometrie Mössbauer (57Fe) de FeMo2S4

We have investigated FeMo₂S₄ by transmission Mössbauer spectroscopy on the ⁵⁷Fe nucleus between 4.2 and 1037 K, using both powdered and single crystal samples.The temperature dependences of the isomer shift and the quadrupole splitting indicate the existence of ferrous ions with well localized 3d electrons. The two different crystallographic Fe sites cannot be separated over the experimental temperature range. The local symmetry of the iron site is lower than axial (η ~ 0.47) and the crystal field splittings Δ₁ and Δ₂ of the Fe²⁺ ? T_2g Orbitals, estimated by the Ingalls' method, are close to 250 and 900 cm^?1.The hyperfine field makes an angle of 14° with the normal on the plane (a, b), deviating a little from the direction of the magnetic moments determined to be perpendicular to (a, b) by neutron diffraction study.At higher temperatures, and more particularly near T_N, a line broadening is observed, and the spectra have to be fitted by a hyperfine field distribution. The broadening comes from the presence of about 7% “abnormal” Fe-sites observed in the paramagnetic spectra, and whose origin is discussed.The Néel temperature was determined to be 112 ± 1 K for the powdered sample and 106 ± l K for the single crystal.     

Formation of intersystem crossing transitions in Pd(II) and Pt(II) porphyrins: Nonplanar distortions of the macrocycle and charge transfer states

We found new bands in the absorption spectra of Pt(II) and Pd(II) complexes of octaethylporphyrin and tetraphenylporphyrin that differ in the nature, number, and position of their side substituents. The bands are observed at 295 K in the range 570–690 nm and are attributed to spin-forbidden transitions from the ground S ₀ state to the excited T ₁ and T ₂ triplet states (the internal heavy atom effect). We determined the frequency distribution, number, and nature of these transitions, as well as their extinction coefficients (? = 6.0–210.0 M^?1 cm^?1), using computer decomposition of complex contours into Gaussian components and additional data obtained from the phosphorescence and phosphorescence excitation spectra of these complexes (295–77 K). In comparison to Pd complexes of porphyrins with planar macrocycles, nonplanar distortions of the tetrapyrrole macrocycle in the ground S ₀ state of the sterically hindered PdOETPP molecule cause a bathochromic shift of the bands of the electronic spin-forbidden S ₀ → T ₁ and S ₀ → T ₂ transitions, as well as an increase in their extinction coefficients. For the PdOEP-Ph(o-NO₂) molecule, which contains the electron acceptor nitro group, an absorption band attributed to an electronic transition from the ground state S ₀ to a charge transfer state (λ_max = 905 nm, ? = 10.0 M^?1 cm^?1) is observed at 295 K.     

External heavy atom effect on the triplet state of aromatic hydrocarbons: IV. Fluorene,triphenylene-d12 and coronene

The phosphorescence decay functions and spectra of ethanol solutions of triphenylene-d₁₂, coronene and fluorene were observed in the presence of different KI concentrations at 77 K. The analysis of the dependence of phosphorescence (T₁ → S₀) rate constant, k_PT, and intersystem crossing (T₁ ? S₀) rate constant, k_GT, on triplet energies E_T of aromatic molecules and on the distance between the heavy atom and the aromatic molecule show that the external heavy atom effects on k_PT and k_GT are essentially of the second and third order, respectively. The phosphorescence spectra of triphenylene and coronene show the presence of the third order contributions in the radiative transition, which involves the second triplet state of aromatic molecule.