Millimeter-Wave and High-Resolution Infrared Spectra of Monoisotopic SCSe: Equilibrium, Ground State, and ν1, mν2, and nν3 Rovibrational Parameters

The Fourier transform infrared spectrum of monoisotopic SC⁸⁰Se has been investigated in the ν₂, ν₃, 2ν₂, 2ν₃, and ν₁ regions with a resolution between 3 and 4 × 10⁻³ cm⁻¹. In addition, the millimeter-wave spectrum has been studied in the region 150 to 320 GHz, and ground and ν₂ = 1 excited state transitions have been measured. Ground state constants, B₀ = 2043.285 4(4) MHz and D₀ = 146.53(5) Hz, have been determined from a merge of millimeter-wave data and ground state combination differences spanning J values up to 77 and 143, respectively. The band centers ν₂ = 352.341 075(9) cm⁻¹ and ν₃ = 505.480 06(5)cm⁻¹ have been determined. The rovibrational parameters of numerous overtone and combination levels (ν₁ν^l2₂ν₃) = 02⁰0, 02²0, 03¹0, 03³0, 04⁰0, 04²0, 00⁰2, and 00⁰3 have been obtained from polynomial analyses whose standard deviations ranged from 0.7 to 3.5 × 10⁻⁴ cm⁻¹. The 10⁰0 level, ν_eff 1435.840 cm⁻¹, is anharmonically perturbed by the 04⁰0 level, with an avoided crossing at J = 55, and W₁₂₂₂₂ = 0.963 09(1) cm⁻¹. Transitions to both the upper (E⁺) and lower (E⁻) sublevels of the dyad were observed for 1 ≤ J′ ≤ 117 and 4 ≤ J′ ≤ 171, respectively, and the deperturbed wavenumbers ν₁ = 1435.542 76(2) and 4ν⁰₂ = 1432.725 00(3) cm⁻¹ were derived. Furthermore, a local crossing of the E⁻ and 04²0 levels involving l-type resonance was observed at J = 91.     

Li mobility in Li0.5 − xNaxLa0.5TiO3 perovskites (0 ≤ x ≤ 0.5): Influence of structural and compositional parameters

The dependence of Li mobility on structure and composition of Li_0.5 − xNa_xLa_0.5TiO₃ perovskites (0 ≤ x ≤  0.5) has been investigated by means of neutron diffraction, nuclear magnetic resonance and impedance spectroscopy. At 300 K, all samples display a rhombohedral superstructure (R-3c S.G.), where octahedra are out of phase tilted along [111] direction of the ideal cubic cell. The elimination of the octahedral tilting is responsible for the rhombohedral–cubic transformation, detected near 1000 K. In these perovskites, La and Na cations are randomly distributed in A sites, but Li ions are fourfold coordinated at unit cell faces of the cubic perovskite. Lithium conductivity, σ_300 K, decreases with the sodium content, decreasing from values typical of fast ionic conductors, 10^− 3 S/cm, to those of good insulators, 10^− 10 S/cm, when the interconnectivity between vacant A sites is lost (x > 0.3). In samples with x < 0.3, dc conductivity displays a non-Arrhenius behaviour, decreasing activation energy from ~ 0.37 to 0.25 eV when the sample is heated between 77 and 500 K. The temperature dependence of B_Li factors shows the existence of two regimes for Li motion. Below 373 K, Li ions remain partially located near square oxygen windows that connect contiguous A sites, but above 400 K, extended Li motions become dominant. The additional decrease of activation energy from 0.25 to 0.16 eV (low-temperature ⁷Li NMR value), should require the full elimination of octahedral tilting which is only produced above 1000 °C.     

Water incorporation into the Ba2(In1 − xMx)2O5‪ (M = Sc 0 ≤ x < 0.5 and M = Y 0 ≤ x < 0.35) system and protonic conduction

Ba₂(In_1 − xM_x)₂O_{5 − y / 2}(OH)_y‪□_{1 − y / 2} (y ≤ 2; M = Sc³⁺ 0 ≤ x < 0.5 and M = Y³⁺ 0 ≤ x < 0.35) compounds were prepared by reacting Ba₂(In_1 − xM_x)₂O₅‪ phases with water vapor. This reaction is reversible. Analyses of the hydration process by TG and XRD studies show that the thermal stability of hydrated phases increases when x increases and that the incorporation of water is not a single-phase reaction inducing either a crystal system or space group modification. Fully hydrated (y = 2) and dehydrated (y = 0) samples have been stabilized at room temperature and characterized for all compositions. In wet air, all phases show a proton contribution to the total conductivity at temperatures between 350 and 600 °C. At a given temperature, proton conductivity increases with the substitution ratio and reaches at 350 °C, 5.4 10^− 3 S cm^− 1 for Ba₂(In_0.65Sc_0.35)₂O_4.2□_0.2(OH)_1.6.     

Oxygen nonstoichiometry of Sr(Co,Fe)O3−δ-based perovskites: I. Coulometric titration of SrCo0.85Fe0.10Cr0.05O3−δ by the two-electrode technique

The p(O₂)–T–δ diagram of perovskite-type SrCo_0.85Fe_0.10Cr_0.05O_3−δ was determined by the coulometric titration technique in the temperature range 770–1250 K at oxygen partial pressures from 8 10⁻¹⁰ to 0.5 atm. Stability of the cubic perovskite phase of SrCo_0.85Fe_0.10Cr_0.05O_3−δ, existing down to the oxygen pressures of 10⁻³–10⁻⁵ atm, was found to be slightly higher than that of SrCo_0.80Fe_0.20O_3−δ, probably due to stabilization of oxygen octahedra neighboring Cr⁴⁺ cations. When the oxygen nonstoichiometry of the Cr-containing perovskite decreases from 0.47 to 0.38, the partial molar enthalpy and entropy for overall oxygen incorporation reaction vary in the ranges −165 to −60 kJ mol⁻¹ and 90 to 150 J mol⁻¹ K⁻¹, respectively. Within the stability limits of the single perovskite phase, the p(O₂)–T–δ diagram can be adequately described by equilibrium processes of oxygen incorporation, cobalt disproportionation and interaction of cobalt and iron cations, with the thermodynamic functions independent of defect concentrations. Increasing grain size in SrCo_0.85Fe_0.10Cr_0.05O_3−δ ceramics from submicron size to 100–200 μm has no effect on the oxygen thermodynamics. The two-electrode coulometric titration technique, based on the alternate use of electrodes for oxygen pumping and e.m.f. measurements, is described and verified by studying oxygen nonstoichiometry of La_0.3Sr_0.7CoO_3−δ and PrO_x.     

Fourier Transform Spectroscopy of theYΣ–XΠiTransition of CuO

TheY²Σ⁺–X²Π_inear-infrared electronic transition of CuO was observed at high resolution for the first time. The spectrum was recorded with the Fourier transform spectrometer associated with the McMath–Pierce Solar Telescope at Kitt Peak. The excited CuO molecules were produced in a low pressure copper hollow cathode sputter with a slow flow of oxygen. Constants for theY²Σ⁺states of CuO are:T₀= 7715.47765(54) cm⁻¹,B= 0.4735780(28) cm⁻¹,D= 0.822(12) × 10⁻⁶cm⁻¹,H= 0.46(10) × 10⁻¹⁰cm⁻¹, γ = −0.089587(42) cm⁻¹, γ_D= 0.1272(79) × 10⁻⁶cm⁻¹,b_F= 0.12347(22) cm⁻¹, andc= 0.0550(74) cm⁻¹. ImprovedX²Π_iconstants are also presented.     

Study on the second-harmonic-generation of GdCa4O(BO3)3 crystals along various phase-matching directions

In this paper, the theoretical calculations of d_eff of GdCa₄O(BO₃)₃ (GdCOB) along various phase-matching (PM) directions are reported. It is shown that the maximum d_eff is out of the main planes and the d_eff in the range of (0<θ≤90, 90<φ≤180) are larger than that in the range of (0<θ≤90, 0≤φ≤90). The PM direction along (θ=66.8, φ=132.6) for GdCOB crystal has the largest d_eff. Second-harmonic-generation (SHG) experiments were performed on GdCOB crystal along various PM directions. The results show that in GdCOB crystal, the intracavity SHG conversion efficiency is 27.6% along the PM direction (θ=66.8, φ=132.6) which is larger than that along PM directions in XY and XZ main planes, which are in good agreement with the theoretical calculations. The continuous-wave (cw) green laser output power is 1.22 W when LD pump power is 10 W in the Nd:YVO₄/GdCOB laser.     

Chemical diffusivity of BaTiO3−δ: I. Experimental determination

The chemical diffusivity of ‘undoped' polycrystalline BaTiO_3−δ was determined via a conductivity relaxation technique, at elevated temperatures (800≤T/°C≤1100) as a function of the ambient oxygen partial pressure in the range of 10⁻¹⁶≤P_O2/atm≤1 including an n- to p-type transition regime. Mathematical formulation was developed to convert conductivity relaxation to the corresponding nonstoichiometry (δ) relaxation in the transition regime. It has been found that the chemical diffusivity appears to exhibit a maximum at the n-to-p transition point where the electronic minimum conductivity falls, and that surface reaction becomes more rate-determining than diffusion as the transition point is approached from both n-type and p-type branches. Experimental details are given and the results are exhaustively compared with those reported up to date on the ‘undoped' BaTiO₃.     

Superconductivity magnetism and low temperature specific heat in YBa2(Cu1−xFex)3O7−δ with δ0 and δ1

Magnetic and low temperature specific heat measurements have been performed on iron doped YBa₂(Cu_1−xFe_x)₃O_7−δ samples with different oxygen contents (δ0 and δ1). Iron doping induces an orthorhombic to tetragonal transition and a decrease of both T_c and diamagnetic signal. Low temperature specific heat measurements reveal a Schottky type anomaly for δ0 samples with x=0.01 (1.8 K) and x=0.02 (3 K). This anomaly is attributed to magnetic interactions within iron limited chains. A numerical analysis of this effect is proposed.     

Effects on structure and superconductivity for La and Ca codoping in YBa2Cu3Oy cuprates

The nominal composition of Y_0.8Ca_0.2Ba_2−xLa_xCu₃O_y (YBLCO) cuprates with x≤0.50 has been synthesized by the standard solid state reaction technique. X-ray diffraction and the resistivity measurements are used to characterize the structure and the superconductivity of YBLCO cuprates. There is no structural phase transition in the whole doping range. The dependencies of the lattice constants and some other structural parameters on the content of La for the samples YBLCO with x≤0.20 are different than those for the samples with x≥0.25. The zero resistance temperature T_c0 increases with the increase of the content of La in YBLCO as x≤0.20, and decreases as x≥0.25. We compared these results with those of Nd-doped Y_0.8Ca_0.2Ba_2−zNd_zCu₃O_y cuprates. It seems that T_c0 is related to the structural parameters due to Ca and La codoping in YBLCO.     

Weak ferromagnetism in BiFeO3 doped with titanium

The Bi_1−xA_xFe_1−xTi_xO₃ (A—Ca, Sr, Pb, Ba) and BiFe_1−xTi_xO_3+δ systems have been studied using X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that all Bi_1−xA_xFe_1−xTi_xO₃ solid solutions are rhombohedral up to x=0.3. In the case of BiFe_1−xTi_xO_3+δ the rhombohedral distortion preserved up to x=0.11. A homogeneous weakly ferromagnetic state was found for Bi_1−xCa_xFe_1−xTi_xO₃ (0.15≤x≤0.25) and BiFe_1−xTi_xO_3+δ (0.06≤x≤0.11), probably due to magnetoelectric interactions, whereas Bi_1−xA_xFe_1−xTi_xO₃ (A—Sr, Pb, Ba) compounds above doping level x>0.1 seem to be collinear antiferromagnets.     

Structural properties and Raman spectroscopy of orthorhombic (Eu1−xPrx)0.6Sr0.4MnO3 (0≤x≤1.0)

The effect of Pr doping on structural properties and room temperature Raman spectroscopy measurements is investigated in manganites (Eu_1−xPr_x)_0.6Sr_0.4MnO₃ (0≤x≤1.0) with fixed carrier concentration. The result of the Rietveld refinement of x-ray powder diffraction shows that these compounds crystallize in an orthorhombic distorted structure with a space group Pnma. It is evident that, with increasing Pr substitution, three types of orthorhombic structures can be distinguished. The phonon frequencies of the three main peaks, in room temperature Raman-scattering measurements, have been discussed together with their structural characteristics, such as bond-length, bond-angles, and the change of orthorhombic structure type. With the increase of Pr content, the mode at 491  cm⁻¹ also shows a corresponding change. A step effect becomes evident, which seems to indicate the close dependence between the frequency shift of this mode and the change in crystal symmetry. This further supports the notion that the mode at 491  cm⁻¹ is closely correlated with the Jahn–Teller distortion. Moreover, we have found that the lowest frequency peak (assigned as an A_1g phonon mode) depends linearly on the tolerance factor t.     

Influence of oxygen growth pressure on laser ablated Cr-doped In2O3 thin films

We present a systematic investigation of the effects of oxygen growth pressure on the structural, optical, and electrical properties of In₂O₃:Cr thin films grown by pulsed laser deposition. X-ray diffraction analysis showed increases in lattice constant from 10.103 Å to 10.337 Å, and in particle size from 13.9 nm to 35.5 nm as the oxygen growth pressure increased from 7.5 × 10⁻⁶ Torr to 7.5 × 10⁻³ Torr, respectively. The observed shift in the X-ray diffraction peaks to lower angles was assumed to be caused by the reduction in the lattice defect density, precisely oxygen vacancies. The optical transparency increased with partial oxygen pressure (P_O2), and an average transmittance of 85% was obtained at 7.5 × 10⁻³ Torr. The films are highly conducting with resistivity as low as 2 × 10⁻⁴ Ω cm and mobility as high as 133 cm/V s. Temperature dependent resistivity measurements in the 45 < T < 300 K temperature range reveal that films grown at 7.5×10⁻⁶≤P_O2≤7.5×10⁻⁴ Torr exhibit negative temperature coefficient of resistivity (TCR) below approximately T = 60 K, T = 120 K, T = 160 K; then positive TCR in the temperature intervals 60 < T < 300 K, 120 < T < 300 K, and 160 < T < 300 K, respectively. This suggests that two disparate mechanisms govern electrical dc transport in the two temperature regions. Film grown at P_O2 of 7.5 × 10⁻³ Torr displayed typical semiconducting behavior with negative TCR in the whole temperature region.     

Measurement and analysis of the ν4 band of silane

The ν₄ band of silane has been recorded with a resolution of about 0.06 cm⁻¹ in the region from 850 to 950 cm⁻¹. Assignments of all allowed transitions in this range with J′ ≤ 12 have been made on the basis of frequency and relative intensity. Qualitative agreement with theory is good but quantitative agreement begins to break down above J′ = 8. The breakdown is attributed to the effects of the strong Coriolis interaction with nearby ν₂.Lines of ²⁹SiH₄ and ³⁰SiH₄ have been observed in the R branch with constant isotope shifts of −1.334 cm⁻¹ and −2.600 cm⁻¹.     

The microwave spectrum and rotational structure of the Δ and Σ electronic states of sulfur monoxide

The spectrum of ¹Δ and ³Σ SO has been studied in the millimeter and submillimeter region of the microwave spectrum. This expanded spectral coverage has made possible the measurement of twenty-two previously unobserved transitions, several of which are necessary for an accurate calculation of the energy levels. As a result, it is now possible to calculate the rotational transitions between energy levels for which J ≤ 10 in both the ground ³Σ electronic state and the excited ¹Δ electronic state to an accuracy comparable to that of the microwave measurements themselves ( 1 MHz). Among the molecular constants calculated are; for the ¹Δ state: B₀ = 21 295.405 MHz, D₀ = 0.0350 MHz, ω_e = 1108 cm⁻¹, and r₀ = 1.4920 Å; and for the ³Σ state: B₀ = 21 523.561 MHz, D₀ = 0.03399 MHz, λ₀ = 158 254.387 MHz, γ₀ = −168.342 MHz, ₀ = 0.305 MHz, r₀ = 1.4840 Å, B_e = 21 609.552 MHz, λ_e = 157 779.2 MHz, and r_e = 1.4811 Å.     

Influence of octahedral tilting and composition on electrical properties of the Li0.2 − xNaxLa0.6TiO3 (0 ≤ x ≤ 0.2) series

The Rietveld analysis of ND patterns of polycrystalline Li_0.2 − xNa_xLa_0.6TiO₃ (0 ≤ x < 0.2) samples, recorded between 300 and 1075 K, shows an orthorhombic–tetragonal transformation, in which the octahedral tilting along the b axis is eliminated at ~ 773 K, but the vacancy ordering along the c axis remains. In Li rich samples, conductivity (10^− 3 Ω^− 1 cm^− 1 at 300 K) departs from the Arrhenius behaviour, decreasing activation energies from 0.37 to 0.14 eV when octahedral tilting is eliminated. Successive Maxwell–Wagner blocking processes, detected in the real part of dielectric constant plots, have been ascribed to the Li blocking at interior domains, grain-boundary and electrode–electrolyte interfaces. The substitution of Li⁺ by Na⁺ decreases the amount of vacant A-sites, decreasing several orders of magnitude the conductivity when the amount of vacancies approaches the vacancy percolation threshold (n_p = 0.27). Below the percolation threshold, Li ions only display local mobility, remaining confined into small domains of perovskites.     

The bending energy levels of C2H2

Absorption spectra of C₂H₂ have been recorded between 50 and 1450 cm⁻¹, with a resolution always better than 0.005 cm⁻¹, using two different Fourier transform spectrometers. Analysis of the data provided two sets of results. First, the bending levels with Σ_t V_t(t = 4, 5) ≤ 2 were characterized by a coherent set of 34 parameters derived from the simultaneous analysis of 15 bands, performed using a matrix Hamiltonian. The following main parameters were obtained (in cm⁻¹): ω₄⁰ = 608.985196(14), ω₅⁰ = 729.157564(10); B₀ = 1.17664632(18), α₄ = −1.353535(86) × 10⁻³, α₅ = −2.232075(40) × 10⁻³; q₄⁰ = 5.24858(12) × 10⁻³, and q₅⁰ = 4.66044(12) × 10⁻³, with the errors (1σ) on the last quoted digit. Second, a more complete set of bending levels with Σ_t V_t ≤ 4, some of which have never previously been reported, and also including V₂ = 1 have been fitted to 80 parameters. This simultaneous fit involved 43 bands and used the same full Hamiltonian matrix. Some perturbations which affect the higher excited levels are discussed.     

Blue cathodoluminescence from thulium implanted AlxGa1−xN and InxAl1−xN

Room temperature cathodoluminescence (RTCL) was obtained from Tm implanted Al_xGa_1−xN with different AlN contents (in the range 0≤x≤0.2) and from implanted In_xAl_1−xN with different InN contents (x=0.13 and 0.19) close to the lattice match with GaN. The Tm³⁺ emission spectrum depends critically on the host material. The blue emission from Al_xGa_1−xN:Tm peaks in intensity for an AlN content of x0.11. The emission is enhanced by up to a factor of 50 times with an increase of annealing temperature from 1000 to 1300 C. The blue emission from In_0.13Al_0.87N:Tm, annealed at 1200 C, is more than ten times stronger than that from Al_xGa_1−xN:Tm, x≤0.2. However, the intensity decreases significantly as the InN fraction increases from 0.13 to 0.19.     

Line Positions and Intensities of the ν1+ ν2+ 3ν3, ν2+ 4ν3, and 3ν1+ 2ν2Bands of Ozone

Using a Fourier transform spectrometer, we have recorded the spectra of ozone in the region of 4600 cm⁻¹, with a resolution of 0.008 cm⁻¹. The strongest absorption in this region is due to the ν₁+ ν₂+ 3ν₃band which is in Coriolis interaction with the ν₂+ 4ν₃band. We have been able to assign more than 1700 transitions for these two bands. To correctly reproduce the calculation of energy levels, it has been necessary to introduce the (320) state which strongly perturbs the (113) and (014) states through Coriolis- and Fermi-type resonances. Seventy transitions of the 3ν₁+ 2ν₂band have also been observed. The final fit on 926 energy levels withJ_max= 50 andK_max= 16 gives RMS = 3.1 × 10⁻³cm⁻¹and provides a satisfactory agreement of calculated and observed upper levels for most of the transitions. The following values for band centers are derived: ν₀(ν₁+ ν₂+ 3ν₃) = 4658.950 cm⁻¹, ν₀(3ν₁+ 2ν₂) = 4643.821 cm⁻¹, and ν₀(ν₂+ 4ν₃) = 4632.888 cm⁻¹. Line intensities have been measured and fitted, leading to the determination of transition moment parameters for the two bands ν₁+ ν₂+ 3ν₃and ν₂+ 4ν₃. Using these parameters we have obtained the following estimations for the integrated band intensities,S_V(ν₁+ ν₂+ 3ν₃) = 8.84 × 10⁻²²,S_V(ν₂+ 4ν₃) = 1.70 × 10⁻²², andS_V(3ν₁+ 2ν₂) = 0.49 × 10⁻²²cm⁻¹/molecule cm⁻²at 296 K, which correspond to a cutoff of 10⁻²⁶cm⁻¹/molecule cm⁻².     

The insertion of magnesium into α-U3O8

The chemical and electrochemical insertion of magnesium into α-U₃O₈ was achieved at ambient and elevated temperatures with the topochemical formation of a product Mg_xU₃O₈ (0<x<0.65). Galvanometric discharges in both non-aqueous and aqueous cells show the existence of two single phase regions at 0.20≤x≤0.27 and x≥0.40. These regions shifted to higher x-values when the discharge was performed at 100°C with DMF as the electrolyte solvent. A fcc phase (a ≈ 5.42 Å) was identified in the cathodic products when cells were discharged beyond x ≈ 0.65. This could be related to the known high temperature fluorite phase Mg_xU_1−xO_2±y. Equilibrium potential measurements were made to determine the integral free energy of magnesium insertion. Kinetic measurements showed magnesium diffusivity in Mg_xU₃O₈ to be three to four orders of magnitude less than that for lithium in the compound Li_xU₃O₈.     

Non-Kramers ENDOR and ESEEM of the S = 2 Ferrous Ion of [Fe(II)EDTA]

We report here the first non-Kramers (NK) ESEEM and ENDOR study of a mononuclear NK center, presenting extensive parallel-mode ESEEM and ENDOR measurements on the S_t = 2 ferrous center of [Fe(II)ethylenediamine-N,N,N′,N′-tetraacetato]²⁻; [Fe(II)EDTA)]²⁻. The results disclose an anomalous equivalence of the experimental patterns produced by the two techniques. A simple theoretical treatment of the frequency-domain patterns expected for NK-ESEEM and NK-ENDOR rationalizes this correspondence and further suggests that the very observation of NK-ENDOR is the result of an unprecedentedly large hyperfine enhancement effect. The mixed nitrogen–carboxylato oxygen coordination of [Fe(II)EDTA]²⁻ models that of the protein-bound diiron centers, although with a higher coordination number. Analysis of the NK-ESEEM measurements yields the quadrupole parameters for the ¹⁴N ligands of [Fe(II)EDTA]²⁻, K = 1.16(1) MHz, 0 ≤ η ≤ 0.05, and the analysis indicates that the electronic zero-field splitting tetragonal axis lies along the N–N direction.