The vibrational spectrum of the OCS molecule based on the data on spectra of liquid and cryosolutions

The IR absorption spectra of liquid OCS (T = 135(1) K) and of the following solutions—OCS + Ar (T = 90 K), OCS + N₂ (T = 90 K), OCS + Kr (T = 130 K), and OCS + Xe (T = 163 K)—are measured in the range 800–7000 cm^?1. From 16 to 40 bands corresponding to transitions to vibrational states up to the third order inclusive are interpreted for basic isotope modification and for the isotopically substituted molecules ¹⁸O¹²C³²S, ¹⁶O¹³C³²S, and ¹⁶O¹²C³⁴S. In the spectra of the liquids, the spectral moments M(1) and M(2) of all the observed bands are determined. The harmonic frequencies ω _i and the anharmonicity constants x _ik are calculated for all the systems, including the liquid. The anharmonicity is found to be constant within the experimental error. A large shift Δω₃ is primarily determined by the dipole-induced dipole interaction.     

Disordering effects and property changes in fast neutron irradiated YIG

Damage region structure and property changes of YIG irradiated atD=10¹⁸?7.8×10¹⁹ n/cm² were studied. Damage regions at 300 K were found to consist of 1) a core of Fe³⁺ paramagnetic phase (PP) withgΔ=0.8 mm/s; 2) a shell of Fe³⁺ intermediate magnetic phase with heavily distorted bond geometry and <H _eff>≤300 kOe; 3) Fe³⁺ (a, d) surrounded by oxygen vacancies and interstitials. The dose dependence of PP concentration is given byC _PP=1-exp(?βD), yielding PP core radiusr _PP=12,5 Å. Magnetic ordering in PP was found to arise atT _tr=90 K. NGR probabilityf′ under irradiation was found to decrease linearly according to Δf′/f′=?C _PP(D). Net magnetization change was found, using the Gilleo model, to obey an analogous relationship ΔM(T)/M(T)=?C _PP(D).T _c dose dependence is given by ΔT _c/T _c=?0.5×C _PP(D) and can be related to lattice parameter change to yield Δa ₀/a ₀=(1.42±0.04)×10^?4×C _PP(D). External field experiments revealed a complex dependence ofK ₁ on PP concentration, elastic stress field magnitude and a with a minimum atD=10¹⁹ n/cm².     

New aspects on URu2Si2 and CeTIn5 (T=Rh, Ir, Co) observed by high pressure NMR and NQR

NMR and NQR studies on two interesting systems (URu₂Si₂, CeTIn₅) were performed under high pressure. (1) URu₂Si₂: In the pressure range 3.0 to 8.3 kbar, we have observed new ²⁹Si NMR signals arising from the antiferromagnetic (AF) region besides the previously observed ²⁹Si NMR signals which come from the paramagnetic (PM) region in the sample. This gives definite evidence for spatially-inhomogeneous development of AF ordering below T ₀ of 17.5 K. The volume fraction is enhanced by applied pressure, whereas the value of internal field (∼91 mT) remains constant up to 8.3 kbar. In the AF region, the ordered moment is about one order of magnitude larger than 0.03 μB. (2) CeTIn₅: The pressure and temperature (T) dependences of nuclear spin-lattice relaxation rate 1/T ₁ of ¹¹⁵In in CeTIn₅ have shown that the superconductivity (SC) occurs close to an AF instability. From the T dependences of 1/T ₁ and Knight shift below T _c. CeTIn₅ has been found to exhibit non-s wave (probable d wave) SC with even parity and line nodes in the SC energy gap.     

Dynamic phenomena in layer superconducting cuprate and organic metals

Dynamic electron spin resonance (ESR) and extended x-ray absorption edge fine structure (XAFS) measurements suggest that layered organic metals and cuprate superconductors behave similarly. The response to microwave radiation in a modulated external magnetic field indicates that: (i) triplet state, T * ESR is observed below T_c for both; (ii) the condensation of free spin doublet D to T* occurs above the transition temperature to superconductivity T_c (10 ± 1 K for the organic metal (BEDT-TTF)₃Ta₂F₁₁ and 92 to 12 K for YBa₂Cu₃O_7-δ and its rare earth derivatives); (iii) antiferomagnetic (AF) resonance is detected above T_c for the organic metal. Here the exchange field between the aligned AF domains: J_AF(150 K) = 130.7 mT (153 mK) is greater than the exchange term J(150 K) ≈ 15 mT (20 mK) between free spins (S = 1/2) leading to T* states; the lifetime of AF domains τ_AF decreases below 150 K and resonance is not detected below 44 K (i.e. τ_AF < 10^-10 s) allowing a superconducting transition to appear below 10 K; (iv) the relaxation time τ₁ for the half field, triplet state ESR absorption increases fourfold near 10 K for the organic metal and, (v) the onset of superconductivity is detected in all superconductors by the appearance of an energy loss at exactly H=0 and, magnetization oscillations observed versus H below T_c when the samples are cooled in a non-zero field H. The spin-lattice relaxation time for the organic metal triplet state, half field ESR near 10 K is interpreted using the Gorter phenomenological relation τ₁ = C_H /α_H, C_H and α_H are respectively the heat capacity and the thermal contact coefficient to the lattice by the spin system, at constant field H . Complementary changes in x-ray edge widths near T_c are correlated to electron-phonon interactions.     

NMR and NQR studies of spin dynamics and superconductivity in High-T c oxides

The magnetic and superconducting properties in the high-T _c cuprates have been investigated over a wide hole doping range by⁶³Cu,¹⁷O and²⁰⁵Tl NMR and NQR in the lightly-doped La_2?xSr_xCuO₄ (LSCO), the heavily-doped Tl₂Ba₂CuO_6+y (TBCO) and the Zn-doped YBa₂Cu₃O₇ (YBCO₇). In low doping region, the large antiferromagnetic (AF) spin correlation around the zone boundary (q=Q) causes the Curie-Weiss behavior of⁶³(1/T ₁ T) associated with that of the staggered susceptibility χ_O(T) in LSCO. In the vicinity of the hole content whereT _c has a peak, the AF spin correlation still survives, although the magnetic coherence length ξ_M is considerably short being presumably (ξ_M/a) ～ 1. The further doping destroys progressively the AF spin correlation, which is no longer present is non-superconducting TBCO compounds. These NMR evidences signify that there is an intimate relation between the presence of the AF spin correlation and the onset of the superconductivity. The local collapse of AF spin correlation is a primary cause for the unexpected strong reduction ofT _c in case of the substitution of Zn impurities into the CuO₂ plane. The superconducting properties clarified by NMR experiments cannot be accounted for by the conventional BCS model or other isotropic s-wave models. A d-wave model is applicable in interpreting consistently most of the NMR results, if the finite density of states at the Fermi level is taken into consideration and is associated with the pair breaking effect. There are increasing evidences that the magnetic mechanism for the superconductivity is promising in high-T _c cuprates.     

Phase separation, ferromagnetism and magnetic irreversibility in La1−xSrxMn1−yFeyO3

Magnetic susceptibility, χ(T), is investigated in ceramic La_1−xSr_xMn_1−yFe_yO₃ (LSMFO) samples with x=0.3 and y=0.15−0.25. A ferromagnetic (FM) transition observed in LSMFO is accompanied with an appreciable decrease of the transition temperature with increasing y, which is connected to breaking of the FM double-exchange interaction by doping with Fe. Strong magnetic irreversibility, observed in low (B=10 G) field, gives evidence for frustration of the magnetic state of LSMFO. The FM transition, which is expanded with increasing B, is more pronounced in the samples with y=0.15-0.20 and broadens considerably at y=0.25, where the irreversibility is increased. Well above the transition, χ(T) exhibits a Curie-Weiss asymptotic behavior, yielding very large values of the effective Bohr magneton number per magnetic ion, incompatible with those of Mn or Fe single ions. At y=0.15 and 0.20 a critical behavior of χ⁻¹(T)∼(T/T_C−1)^γ in the region of the FM transition is characterized by influence of two different magnetic systems, a 3D percolative one with γ₌γ_p≈1.8 and T_C=T_C^(p), and a non-percolative 3D Heisenberg spin system, with γ=γ_H≈1.4 and T_C=T_C^(H), where T_C^(p)<T_C^(H). At y=0.25 the percolative contribution to the critical behavior of χ(T) is not observed. The dependence of χ on T and y gives evidence for phase separation, with onset already near the room temperature, leading to generation of nanosize FM particles in the paramagnetic host matrix of LSMFO. The ferromagnetism of LSMFO is attributable to percolation over the system of such particles and generation of large FM clusters, whereas the frustration is governed presumably by a system of smaller weakly-correlated magnetic units, which do not enter the percolative FM clusters.     

Manifestation of vortex depinning transition in nonlinear current-voltage characteristics of polycrystalline superconductor Y1−xPrxBa2Cu3O7−δ

We present our recent results on the temperature dependence of current-voltage characteristics for polycrystalline Y_1−xPr_xBa₂Cu₃O_7−δ superconductors with x=0.0, 0.1 and 0.3. The experimental results are found to be reasonably well fitted for all samples by a power like law of the form V=R(I−Ic)^a(T). Here, we assume that a(T)=1+Φ₀IC(T)/2πkBT and IC(T)=IC(0)(1−T/TC)^3/2 for the temperature dependences of the power exponent and critical current, respectively. According to the theoretical interpretation of the obtained results, nonlinear deviation of our current-voltage characteristics curves from Ohmic behavior (with a(TC)=1) below TC is attributed to the manifestation of dissipation processes. They have a characteristic temperature Tp defined via the power exponent as a(Tp)=2 and are related to the current induced depinning of Abrikosov vortices. Both TC(x) and Tp(x) are found to decrease with an increase of Pr concentration x reflecting deterioration of the superconducting properties of the doped samples.     

Self,nitrogen and oxygen broadening of the 115-GHz line of carbon monoxide

Self nitrogen, oxygen and air-broadened half-widths of the 115-GHz line of CO have been measured at various temperatures between 293 K (room temperature) and 220 K. The temperature dependence of the broadening parameter CCO-XW is described by a power law CCO-XW (T) = CCO-XW(293 K)(T/293)-n co-x. The values of CCOW (293 K) and nCO-X are presented for each broadening gas X, X - CO, N2 and O2. The usual relation CCO-airW (T) = 0.78CCO−N2W(T) + 0.21CCO−O2 W(T) is found to be valid in the temperature and pressure ranges of the present experiments.     

Diode laser measurements of strengths,half-widths,and temperature dependence of half-widths for CO2 spectral lines near 4.2 μm

Absolute line strengths have been measured at room temperature for spectral lines in the R branch of the ν₃ band of ¹²C¹⁶O₂, ¹²C¹⁶O¹⁸O, and ¹²C¹⁶O¹⁷O and the (ν₂ + ν₃) ? ν₂ and (ν₁ + ν₃) ? ν₁ bands of ¹²C¹⁶O₂ in the region 2365–2393 cm^?1 using a tunable diode laser spectrometer; from these measurements band strengths have been computed. Self- and nitrogen-broadened half-widths have been measured for some ν₃ lines of ¹²C¹⁶O₂ and ¹²C¹⁶O¹⁷O, and nitrogen-broadened half-widths measured for some (ν₂ + ν₃) ? ν₂ band lines of ¹²C¹⁶O₂. From measurements made over a temperature range from 217 to 299 K we have obtained temperature coefficients n, for the N₂-broadened Lorentz half-width defined as $\text{b}{}_{\mathrm{L}}{}^0\text{(T) = b}{}_{\mathrm{L}}{}^0\text{(T}{}_0\text{)(}\text{T}\text{T}{}_0\text{)}{}^{\mathrm{?n}}$, for the ν₃ and (ν₂ + ν₃) ? ν₂ bands of ¹²C¹⁶O₂. They are 0.757 ± 0.008 and 0.789 ± 0.015, respectively.     

Optical absorption spectrum of Cr3+ ion doped in zinc cesium sulphate hexahydrate

Optical absorption spectrum of Cr³⁺ ion doped in zinc cesium sulphate hexahydrate single crystal has been studied both at room and liquid nitrogen temperatures. From the nature and position of the bands a successful interpretation of all the bands could be made assuming octahedral symmetry for the Cr³⁺ ion in the crystal. The observed bands are assigned to the transitions from the ground ⁴A_2g(F) state to the excited ²E_g(G), ²T_1g(G), ⁴T_2g(F) and ⁴T_1g(F) states.The crystal field parameters Dq = 1735 cm^?1, B = 635 cm^?1 and C = 4.75 B are found to give a good fit to the observed band positions.     

Thermal decomposition of toluene: Overall rate and branching ratio

The two-channel thermal decomposition of toluene, C₆H₅CH₃ → C₆H₅CH₂ + H (1) and C₆H₅CH₃ → C₆H₅ + CH₃ (2), was investigated in shock tube experiments over the temperature range of 1400-1780 K at a pressure of 1.5 (±0.1) bar. Rate coefficients for reactions (1) and (2) were determined by monitoring benzyl radical (C₆H₅CH₂) absorption at 266 nm during the decomposition of toluene diluted in argon and modeling the temporal behavior of the benzyl concentration with a kinetic model. The first-order rate coefficients determined at a pressure of 1.5 bar are expressed by k₁(T) = 2.09 × 10¹⁵ exp (−87510 [cal/mol]/RT) [s⁻¹] and k₂(T) = 2.66 × 10¹⁶ exp (−97880 [cal/mol]/RT) [s⁻¹]. The resulting branching ratio, k₁/(k₁ + k₂), ranges from 0.8 at 1350 K to 0.6 at 1800 K.     

Electronic and vibrational absorption spectra in falcondoite

Optical absorption spectrum of Ni²⁺ ion in Falcondoite, a new mineral has been studied at 300 K. From the nature and positions of the observed bands a succesful interpretation of all the bands could be made assuming octahedral symmetry for the Ni²⁺ ion in the crystal. The bands at 9255, 15 380 and 27 390cm⁻¹ are assigned to ³T_2g(F), ³T_1g and ³T_1g(P) and the other band at 24385 cm⁻¹ assigned to ¹T_2g(D). The crystal field and the Racah parameters are evaluated to be Dq = 925 cm⁻¹, B = 1000 cm⁻¹ and C = 4095 cm⁻¹. NIR and IR spectra of the sample are also studied. The fundamental vibrational modes of H₂O are identified in the IR spectrum. The bands observed in the NIR spectrum are due to overtones and combination tones of water molecule.     

In-beam study of high-spin states in199,200,201Po and systematical features of Z=84 polonium isotopes

Excited states in^199,200,201Po were populated in the reactions¹²C+¹⁹⁴Pt and¹²C+¹⁹⁵Pt. The subsequentγ-radiation was studied using conventional in-beam spectroscopic methods. States with spins up to (29/2), 18 and ≧35/2?, respectively, were populated in the three nuclides. Three isomeric states with the following half-lives were observed in²⁰⁰Po:T _1/2(8⁺)=90(15) ns,T _1/2(11^?)=120(20) ns andT _1/2(12⁺)=267(4) ns. The structure of the excited states was interpreted within the framework of the spherical shell model. The three isomers are suggested to be two-quasiparticle states with configurationsπ(h _{2 2})_8J, π(h₉i_13/2)₁₁- and v(i _{1 3/2 ?2})₁₂₊. A self-consistent Hartree-Fock calculation was performed to obtain ground-state deformations of the neighbouring Pb cores. From the results of the experiments and the calculations it was concluded that no appreciable deformations of the cores are manifested in the yrast states of these three Po nuclei.     

Fourier transform spectroscopy of CO2 and OCO in the 3800-8500 cm region and the global modeling of the absorption spectrum of CO2

The absorption spectrum of the ¹⁸O enriched carbon dioxide has been recorded at Doppler limited resolution with a Fourier transform spectrometer in the spectral range 3800-8500 cm⁻¹. Seventeen cold bands (14Σ-Σ and 3Σ-Π) and nine hot bands (9Π-Π) of ¹²C¹⁸O₂, nineteen cold bands (18Σ-Σ and 1Σ-Π) and eighteen hot bands (6Σ-Σ, 9Π-Π and 3Δ-Δ) of ¹⁶O¹²C¹⁸O have been observed. Among them, 14 ¹²C¹⁸O₂ bands and 12 ¹⁶O¹²C¹⁸O bands are observed for the first time. The spectroscopic parameters G_v, B_v, and centrifugal distortion constants, have been determined for all observed bands. Effective Hamiltonian parameters for the ¹²C¹⁸O₂ isotopic species are retrieved from the global fitting of the observed line positions presented in this paper and collected from the literature. As the result, 65 obtained effective Hamiltonian parameters reproduce 5443 observed line positions of 73 ¹²C¹⁸O₂ bands with RMS = 0.00145 cm⁻¹.     

Effect of surface orientation and thickness on the magnetization of anisotropic FCC ferromagnetic films

The dependence on temperature of the layer magnetization of a Heisenberg ferromagnetic ultrathin film in presence of magnetocrystalline single-ion anisotropy was theoretically investigated in the framework of a Green's function approach using the random phase approximation (RPA). The effect of surface orientation and of film thickness N on the Curie temperature T_C was carefully investigated in the case of face centered cubic (FCC) films: the steepest increase of T_C(N) was found in the case of the FCC(1 1 1) orientation and the smoothest in the FCC(1 1 0) one. Our results for T_C(N) were successfully fitted by a finite-size scaling relation [T_C(∞)−T_C(N)]/T_C(N)=(N/N₀)^−λ, giving a shift exponent λ≃1.5, irrespectively of the surface orientation. Finally, the temperature evolution of the magnetization profile was analyzed, as well as its limiting shape at T_C.     

A calorimetric study of the dimerized phase of C60 fullerene

The temperature dependence of the heat capacity at a constant pressure C _p ⁰ = f(T) for the dimerized phase of the C₆₀ fullerene in the temperature range 300–575 K and the thermodynamic characteristics for depolymerization of this phase under normal pressure are investigated using precision differential scanning calorimetry. It is established that thermal depolymerization is a kinetically hindered process. The final products of thermal depolymerization are identified as a partially crystalline monomer face-centered cubic phase of C₆₀ with a degree of crystallinity α = 67 mol %. The results obtained in this study and our previous experimental data on the low-temperature heat capacity are used in the calculations of standard thermodynamic functions for the (C₆₀)₂ crystalline dimer, namely, the heat capacity C _p ⁰ (T), the enthalpy H ⁰(T) ? H ⁰(0), the entropy S ⁰(T), and the Gibbs function G ⁰(T) ? H ⁰(0) in the temperature range from T → 0 to 394 K.     

Spectral measurements of high-temperature isotopic carbon dioxide in the 4.5- and 2.8-μm regions

High-resolution measurements have been made using the AFGL 2-m path difference Fourier transform spectrometer on isotopically enriched samples of carbon dioxide. Two regions were investigated: 2140–2320 and 3470–3770 cm⁻¹. The samples were observed in absorption at temperatures up to 800 K. Observed line positions to high rotational levels were obtained for 15 parallel bands with Δv₃ = 1 for the isotopic variants ¹³C¹⁶O₂, ¹³C¹⁶O¹⁸O, and ¹³C¹⁶O¹⁷O in the 4.5-μm region and for 23 bands of the type Δv₁ = 1, Δv₃ = 1 for the species ¹²C¹⁶O₂, ¹²C¹⁶O¹⁸O, and ¹²C¹⁸O₂ in the 2.8-μm region.     

Stoichiometric synthesis of fullerene compounds with lithium and sodium and analysis of their IR and EPR spectra

A modified method is proposed for preparing fullerene compounds with alkali metals in a solution. The compounds synthesized have the general formula Me _n C₆₀(THF)_x, where Me = Li or Na; n=1–4, 6, 8, or 12; and THF = tetrahydrofuran. The use of preliminarily synthesized additives MeC₁₀H₈ makes it possible to prepare fullerene compounds with an exact stoichiometric ratio between C ₆₀ ^n? and Me ⁺. The IR and EPR spectra of the compounds prepared are analyzed and compared with the spectra of their analogs available in the literature. The intramolecular modes T _u (1)-T _u (4) for the C ₆₀ ^n? anion are assigned. The splitting of the T _u (1) mode into a doublet at room temperature for Me _n C₆₀(THF)_x (n=1, 2, 4) compounds indicates that the fullerene anion has a distorted structure. An increase in the intensity of the T _u (2) mode, a noticeable shift of the T _u (4) mode toward the long-wavelength range, and an anomalous increase in the intensity of the latter mode for the Li₃C₆₀(THF)_x complex suggest that, in the fullerene anion, the coupling of vibrational modes occurs through the charge-phonon mechanism. The measured EPR spectra of lithium-and sodium-containing fullerene compounds are characteristic of C ₆₀ ^? anions. The g factors for these compounds are almost identical and do not depend on temperature. The g factor for the C ₆₀ ^n? anion depends on the nature of the metal and differs from the g factor for the C ₆₀ ^? anion.     

Components of the low-temperature heat capacity of rare-earth hexaborides

The temperature dependence of heat capacity C _p(T) was studied for nine rare-earth hexaborides MB₆(M=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) at temperatures of 5–300 K. Using the correspondence principle for lattice heat capacities of isostructural compounds, the lattice contribution C ₁(T) and the excess contribution ΔC(T) to the heat capacity of the hexaborides were determined. The lattice heat capacity C ₁(T) is represented as the sum of the Debye contributions of the metal and boron sublattices: C ₁(T)=C _M (T)+6C _B(T). The Debye temperatures π_M and π_B of the metal and boron sublattices were determined. The anomalies in the excess heat capacity ΔC(T)=C _p (T)?C ₁(T) are related to the magnetic ordering effects, the Schottky contribution, and the Jahn-Teller effect.