The ν2 and 2ν2 - ν2 bands of N O2: Electron Spin-Rotation and Hyperfine Contact Resonances in the (010) Vibrational State

High-resolution Fourier transform spectra covering the 720-920 cm⁻¹ spectral region have been used to perform a reanalysis of the ν₂ band ((010)-(000) vibrational transition) together with the first analysis of the 2ν₂ - ν₂ hot band of nitrogen dioxide ((020)-(010) vibrational transition). The high-quality spectra show that, for numerous ν₂ lines, the hyperfine structure is easily observable in the case of resonances due to the hyperfine Fermi-type operator. By performing a full treatment of the spin-rotation and of the hyperfine operators, a new line list of the ν₂ band (positions and intensities) has been generated, and it is in excellent agreement with the experimental spectrum. Also, a thorough analysis of the 2ν₂ - ν₂ hot band has been performed leading to an extended set of new (020) spin-rotation levels. These levels, together with the {(100), (020), (001)} spin-rotation levels deduced previously from the analysis of the ν₁, 2ν₂, and ν₃ cold bands performed in the 6.3- to 7.5-μm spectral range [A. Perrin, J.-M. Flaud, C. Camy-Peyret. A.-M. Vasserot, G. Guelachvili, A. Goldman, F. J. Murcray, and R. D. Blatherwick, J. Mol. Spectrosc.154, 391-406 (1992)] were least-squares fitted, allowing one to derive a new set of vibrational band centers and rotational, spin-rotation, and interaction constants for the {(l00)(020)(001)} interacting states of ¹⁴N ¹⁶O₂.     

Far infrared spectral lines and absorptance calculation of NO

The positions and intensities of pure rotation lines of ¹⁴N¹⁶O have been calculated between 10–200 cm^-1 and are tabulated. The line by line absorption spectrum has been computed using tabulated parameters, and compared with experimental spectra measured by other authors. The spectral emission of atmospheric NO has been calculated for an altitude of 14.5 km, where some measurements have been carried out. After comparing the NO and the background H₂O+O₂+O₃ spectra, it is shown that the NO emission in the far i.r. spectrum of the lower stratosphere is negligible.     

First high-resolution analysis of the 4ν1+ν3 band of nitrogen dioxide near 1.5 μm

The high-resolution absorption spectrum of the 4ν₁+ν₃ band of the ¹⁴N¹⁶O₂ molecule was recorded by CW-Cavity Ring Down Spectroscopy between 6575 and 6700 cm⁻¹. The assignments involve energy levels of the (4,0,1) vibrational state with rotational quantum numbers up to K_a=8 and N=48. A large majority of the spin-rotation energy levels were reproduced within their experimental uncertainty using a theoretical model which takes explicitly into account the Coriolis interactions between the spin-rotational levels of the (4,0,1) vibrational state and those of the (4,2,0) and of (0,9,0) dark states, the anharmonic interactions between the (4,2,0) and (0,9,0) states together with the electron spin-rotation resonances within the (4,0,1), (4,2,0) and (0,9,0) states. Precise vibrational energies, rotational, spin-rotational, and coupling constants were determined for the {(4,2,0), (0,9,0), (4,0,1)} triad of interacting states. Using these parameters and the value of the transition dipole-moment operator determined from a fit of a selection of experimental line intensities, the synthetic spectrum of the 4ν₁+ν₃ band was generated and is provided as Supplementary Material.     

Electron spin resonance study of oxygen-17 enriched N,N-dimethyl-4-nitroaniline radical anion

N,N-Dimethyl-d₆-4-nitroaniline enriched to approximately 11 atom. per cent in oxygen-17 has been prepared and the oxygen-17 isotropic hyperfine interaction in the corresponding radical anion has been examined. In dry dimethylformamide solution we find a _O = -8·85 ± 0·02 and a _N = 11·39 ± 0·10 gauss, while in moist acetonitrile solution a _O = -8·82 ± 0·07 and a _N = 12·23 ± 0·11 gauss. These results substantiate the recent suggestion that the isotropic oxygen-17 splittings in π-radicals may be described by a single parameter equation analogous to McConnell's relation for aromatic proton splittings, i.e. a _O = Q _OρO ^π, where Q _O = -41 ± 3 gauss.     

Critical current in Ag/BPSCCO tapes using low purity materials

Silver-clad Bi_1·7Pb_0·4Sr_1·8Ca₂Cu_3·5O _x (BPSCCO) tapes have been fabricated using low purity (98–99%) starting materials and following the powder-in-tube technique. MaximumJ _c values of 6·14 × 10³ A·cm⁻² at 77 K and 1·4 × 10⁵ A·cm⁻² at 4·2 K have been obtained in tapes subjected to the process of intermediate rolling and sintering. The bulk superconducting material used for the tape-fabrication contains both 2223 and 2212 phases in the ratio 60:40. A pure phase material and the optimization of the sintering parameters are expected to yield much higherJ _c values at 77 K. It is possible that the copper-rich phase(s) and/or a small amount of iron impurity (60 ppm) present in CuO might be acting as flux pinning sites and could be responsible for highJ _c values.     

Single-Crystal EPR Identification of a Low Hyperfine Value and Interstitial Position of Copper Impurity in Diaquabis[malonato(1-)-κ2O,O′] Zinc(II)

Electron paramagnetic resonance studies have been carried out at 300 K on the Cu(II)-doped [Zn(C₃H₂O₄)₂(H₂O)₂] system in single-crystal and powder forms in order to rationalize the low parallel ⁶³Cu hyperfine value. Angular variation of the hyperfine resonances in the three orthogonal planes shows the presence of only one magnetic site with g and A values equal to g _zz = 2.455, g _yy = 2.121, g _xx = 2.105 and A _zz = 160.9 · 10⁻⁴ cm⁻¹, A _yy = 12.5 · 10⁻⁴ cm⁻¹, A _xx = 7.35 · 10⁻⁴ cm⁻¹. The crystal structure of the host lattice is isostructural with the corresponding cobalt complex and contains two molecules per unit cell. The low magnitude of A _zz value for the complex is rationalized in terms of an admixture of the ground state with the excited state and delocalization of the unpaired spin density onto the ligands. In addition, the highest hyperfine value obtained from the single-crystal data (160.9 · 10⁻⁴ cm⁻¹) is considerably larger than that obtained from the powder spectrum (138 · 10⁻⁴ cm⁻¹). Authors' address: P. Sambasiva Rao, Department of Chemistry, Pondicherry University, Pondicherry 605014, India     

Transport properties of long monofilamentary Bi(2223) tapes

Summary Monofilamentary Bi(2223) tapes withJ _c(77 K, 0 tesla) up to 30 000 A/cm² have been prepared by cold rolling using the powder-in-tube method. An optimization of the precursor powders has led to a higher phase purity after the reaction heat treatment. The deformation process has been optimized in order to increase the oxide density and to reduce sausaging effects on the oxide thickness. The transport properties of these tapes have been studied in a wide range of temperature (4.2K-T _c) and magnetic fields (up to 28 tesla). The critical-current values at 77 K fields of 0.5 T and 1 T parallel to the tape surface are 10 000 A/cm² and 5400 A/cm², respectively. At 4.2 K theJ _c value decreases from 1.6·10⁵ A/cm² at 0 T to 6·10⁴ A/cm² at 15 T. At fields higher than 15 tesla a very low field dependence ofJ _c has been found, regardless of the tape orientation. Transport properties have also been studied by cutting small sections of the tape in order to investigate the local critical-current distribution. It has been found that, even in rolled tapes of good quality (J _c (77 K, 0 T)>20000 A/cm²), theJ _c distribution is homogeneous: the critical current density increases gradually from the centre of the tape to the sides, the latter exhibiting much higherJ _c (46000 A/cm²) than in the centre (18000 A/cm²). Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.     

Critical current densities of high pressure oxygen sputtered thin films of YBa2Cu3O7−x by non-resonant rf absorption method

The critical current densities (J _c) have been measured at 77K in high pressure oxygen sputtered thin films of YBa₂Cu₃O_7−x superconductor using the non-resonant rf absorption technique. High values ofJ _c (∼ 10⁵ A/cm²) are observed in these relatively large area (∼ 1·2 cm²) films.     

The F+ center in reactor-irradiated aluminum oxide

A point-ion calculation has been performed for the F⁺ center in α-Al₂O₃ (one electron in an O^2? vacancy). Optical transitions are predicted at 2·26, 3·39 and 5·15 eV. Contact hyperfine interactions with the two nearest pairs of Al³⁺ ions are calculated to be 151 and 39 G. Single crystals of α-Al₂O₃ were reactor-irradiated up to doses of 10²⁰ fast neutrons per cm², and studied by electron spin resonance (ESR). A broad ESR spectrum with 13 resolved components at g=2·0029±0·0005 was interpreted as the interaction of an unpaired electron with two pairs of Al³⁺ nuclei with hyperfine constants of 49·2 and 13·5 G. These values are in the same ratio as the values calculated for the F⁺ center, to which this ESR spectrum is attributed. The discrepancy of a factor of three is typical of point-ion calculations. The optical absorption spectrum for heavily-irradiated samples is not available for comparison with calculated transition energies.     

New high-resolution analysis of the {ν1 + ν3} band of the NO2 isotopomer of nitrogen dioxide: Line positions and intensities

The high-resolution Fourier transform absorption spectrum of an isotopic sample of nitrogen dioxide, ¹⁵N¹⁶O₂, was recorded in the 3.4 μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242 (1991) 367-377] a new analysis of the ν₁ + ν₃ band located at 2858.7077 cm⁻¹ has been performed. This new assignment concerns (1 0 1) energy levels involving rotational quantum numbers up to K_a = 10 and N = 54. Using a theoretical model which accounts for both the electron spin-rotation resonances within each vibrational state and the Coriolis interactions between the (1 2 0) and (1 0 1) vibrational states, the spin-rotation energy levels of the (1 0 1) vibrational state could be reproduced within their experimental uncertainty. In this way, the precise vibrational energy, rotational, spin-rotation, and coupling constants were achieved for the {(1 2 0), (1 0 1)} interacting states of ¹⁵N¹⁶O₂. Using these parameters and the transition moment operator which was obtained for the main isotopic species, ¹⁴N¹⁶O₂, a comprehensive list of the line positions and intensities was generated for the ν₁ + ν₃ band of ¹⁵N¹⁶O₂.     

Weak exchange interactions in the heteronuclear crystal CuPr2(CCl3COO)8·6H2O

The new heteronuclear crystal CuPr₂(CCl₃COO)₈·6H₂O, constructed of chains containing copper and praseodymium atoms, has been synthesized and investigated by EPR at 9.3 GHz at temperatures ranging from room temperature down to 10 K. At temperatures T∼300–130 K, EPR spectra are observed which are characteristic of isolated polyhedra of copper ions with g _z=2.330±0.005, g _x,y =2.053±0.005, A _z=139×10⁻⁴ cm⁻¹, and A _x,y <26×10⁻⁴ cm⁻¹. At temperatures T<130 K a complex spectrum is observed, associated with the appearance of weak exchange interactions between the copper ions in the chain (J _Cu-CuΣS _i·S _i+1), comparable in magnitude with the hyperfine interactions J _Cu-Cu=0.015 cm⁻¹ at T=10 K. The magnitude of the exchange interaction decreases smoothly as the temperature is raised. It is conjectured that orbitals of the praseodymium ions participate in the process of indirect exchange between the copper ions. Fiz. Tverd. Tela (St. Petersburg) 41, 2154–2157 (December 1999)     

The Lamb-dip spectrum of the J + 1 ← J (J = 0, 1, 3-8) transitions of HCN: The nuclear hyperfine structure due to H, C, and N

The pure rotational J + 1 ← J transitions, with J = 0, 1, 3-8, of H¹³CN have been observed in the millimeter- and submillimeter-wave region using the Lamb-dip technique to resolve the hyperfine structure due to H, ¹³C, and ¹⁴N. The present observations allow us to provide for the first time the spin-rotation constant of ¹³C and the spin-spin interaction constant S₁₂ (between H and ¹³C) as well as to remarkably improve the quadrupole coupling and spin-rotation constants of ¹⁴N. In addition, a good empirical estimation of C_I(H), based on ab initio calculations, has also been provided. Furthermore, our frequencies together with previous data permit to determine the most accurate ground state rotational parameters known up to now.     

Nuclear hyperfine structure in the XΣ state of ZrC

Electronic band systems of zirconium monocarbide, ZrC, in the 16 000-19 000 cm⁻¹ region have been observed following the reaction of laser-ablated Zr atoms with methane under supersonic free-jet conditions. Rotational analyses of high-resolution spectra have shown that the ground state of ZrC is a ³Σ state, with r₀=1.8066 Å and an unexpectedly small spin-spin parameter, λ=0.5139 cm⁻¹. The spectra are dense because of the five naturally occurring isotopes of Zr. Four of these, with mass numbers 90, 92, 94, and 96, have I=0, but the fifth, ⁹¹Zr, present in 11.22% abundance, has I=5/2. Lines of ⁹¹ZrC can be assigned in some of the strongest bands, and are found to display sizeable hyperfine splittings, with widths of up to 0.2 cm⁻¹. Analysis shows that the largest hyperfine effects are in the ground state, where b=−0.03133±0.00015 cm⁻¹ and c=−0.00123±0.00037 cm⁻¹ (3σ error limits). The large Fermi contact parameter, b, indicates that an unpaired Zr 5sσ electron is present, which, taken together with the small value of λ, means that the ground state must be a ³Σ⁺ state, from the electron configuration (Zr 5sσ)¹ (C 2pσ)¹. Internal hyperfine perturbations occur between the F₁ and F₃ electron spin components of the ground state in the range N=2-4, producing extra lines in some of the branches; the perturbations are of the type ΔN=0, ΔJ=±2, and are a second-order effect arising because the F₁ (J=N+1) and F₃ (J=N−1) spin components both interact with the F₂ (J=N) component through ΔN=0, ΔJ=±1 matrix elements of the Fermi contact operator. Second-order perturbations of this type can only occur in states that are very close to case (b) coupling.     

Contribution to the Analysis of theA2←XA1“Wulf” Transition of Ozone by High-Resolution Fourier Transform Spectrometry

The analysis of the rotational structure of the high-resolution Fourier transform 0⁰₀absorption spectrum of the³A₂←X¹A₁band system of the “Wulf” transition of the isotopomer¹⁶O₃of ozone is reported for the first time. With a near pure case (b) coupling model for the upper triplet state, we have assigned a significant portion of the spectrum, mainly theF₁(J=N+ 1) andF₂(J=N) spin components, primarily in the lower frequency region of the band. The lines corresponding to theF₃(J=N− 1) component are weak at lower frequencies and heavily congested in the central and higher frequency regions of the spectrum. Perturbations and predissociation phenomena have reduced the effective lifetime of the metastable³A₂state and have also limited the number of transitions included in the least-squares fit of the band. Approximately 100 lines have been assigned in the range from 9100–9550 cm⁻¹. Three rotational, three centrifugal distortion, three spin–rotation, and one spin–spin constant were varied. The geometry of the molecule in the³A₂state, as determined from these constants, isr= 1.345 Å and θ = 98.9°, in good agreement withab initioresults.     

Pair exchange interaction in a crystalline nitroxide radical ESR study of dimers in the triplet state

The dimerization of the 9-aza-bicyclo (3,3,1) nonan-3-one-9-oxyl in the solid state is investigated by use of ESR spectroscopy. The ESR spectrum of a single crystal is characteristic of symmetric pairs of exchange-coupled radicals in a thermally accessible triplet state. The presence of well-resolved hyperfine structure is evidence for strongly localized excitations with a jumping rate lower than 10⁷ Hz.

The ESR spectrum is well described by the spin hamiltonian

At 35 GHz the observed splitting of the m _s=+ 1?0 transition has been found to be slightly different from that of the m _s=0?-1 one; this anomaly is explained by the mixing of the m _s electronic states.

The parameters and the principal directions of the zero-field splitting, spectroscopic and hyperfine tensors are determined and discussed. The principal directions of the dipolar tensor indicate a nearly equal spin density on the nitrogen and oxygen atoms; from the fine structure parameters D and E, determined to be (-0·0723 ± 0·0005) cm^-1 and (-0·0044±0·0003) cm^-1 at T=293 K respectively, it is suggested that the unpaired electron is partly delocalized on the molecule.

The singlet-triplet energy gap (J) and the zero-field splitting parameters are shown to be linearly temperature-dependent. These variations with temperature are attributed to the thermal expansion of the crystal lattice.     

Spin-spin interaction of Ni2+ ions in ZnSiF6·6H2O

The angular dependences of the electron spin resonance spectrum of 1% Ni²⁺ ions in a ZnSiF₆·6H₂O matrix are investigated experimentally at 36 GHz and 4.2 K. Besides the main spectrum of the isolated ion, we observed a spectrum due to interacting pairs of Ni²⁺ ions, located in the first (nn) and second (2n) coordination spheres and coupled by, besides the magnetic dipole-dipole interaction, isotropic exchange: J _nn = (−197±1)×10⁻⁴, J _2nα = (−5±1)×10⁻⁴, and J _2nβ = (3±2)×10⁻⁴ cm⁻¹. Lines due to other isolated Ni²⁺ ions, which have a different initial splitting D, are also present in the spectrum with intensity comparable to the pair spectrum. Low-symmetry distortions of the crystal field are observed, caused by a pair of impurity ions located close to one another. It is shown that the previously proposed interpretation is incorrect. Fiz. Tverd. Tela (St. Petersburg) 41, 1602–1608 (September 1999)     

An ab initio calculation of the rotational-vibrational energies in the electronic ground state of NH2

We have calculated ab initio the three-dimensional potential-energy surface of the NH₂ molecule at 145 nuclear geometries spanning energy ranges of about 18 000 cm^-1 for the NH stretch and 12 000 cm^-1 for the bend. The ab initio configuration-interaction calculations were done using the multireference MRD-CI method. The calculated equilibrium configuration has NH bond length r _e = 1·0207 Å and bond angle α = 103·1°. The rotational-vibrational energies for ¹⁴NH₂, ¹⁴NHD and ¹⁴ND₂ were calculated variationally using the Morse-oscillator rigid-bender internal-dynamics Hamiltonian. For ¹⁴NH₂ we calculate that υ₁ = 3267 (3219) cm^-1, υ₂ = 1462 (1497) cm^-1 and υ₃ = 3283 (3301) cm^-1, where experimental values are given in parentheses.     

Far ultra-violet absorption bands of osmium (IV), iridium (IV), platinum (IV) hexahalides

The gas phase electron resonance spectrum of SeO in its ³Σ and ¹Δ states has been studied. Values of the rotational constant B ₀ and ‘spin-spin’ splitting parameter λ in the ³Σ state, previously determined from the ultraviolet spectrum, are shown to be consistent with the electron resonance results, and we are also able to estimate the spin-rotation interaction constant. In addition, the ³Σ spectrum shows ⁷⁷Se hyperfine structure. The ¹Δ spectrum yields values for the rotational constant (and hence bond length) and rotational g factor.     

The local structure and interactions between V4+ ions in soda-phosphate glasses

EPR investigation on xV₂O₅ · (100 −x)[2P₂O₅ · Na₂O] and xV₂O₅ · (100 −x)[P₂O₅ · mNa₂O] (m = 1.5 and 2) glass systems was performed. The changes observed in the EPR spectra of xV₂O₅× (100 −x)[2P₂O₅ · Na₂O] glasses with increasing content of vanadium oxide are explained supposing that these spectra consist of two superposed EPR signals, one with hyperfine structure typical for isolated ions and another one consisting of a broad line without hyperfine structure characteristic for clustered ions. The clustered V⁴⁺ ions are not evidenced at low V₂O₅ contents (x = 5 mol%). The EPR spectra of xV₂O₅ · (100 −x)[P₂O₅ · mNa₂O] glasses indicate a superposition of two or three hyperfine structures attributed to nonequivalent VO²⁺ centers. Spin Hamiltonian parameters (g, A), dipolar hyperfine coupling parameter (P) and Fermi contact interaction term (K) have been evaluated. The ratio between the number of clustered and isolated ions was also determined.     

Fabrication and characterization of 4H—SiC bipolar junction transistor with double base epilayer

In this paper we report on a novel structure of a 4H-SiC bipolar junction transistor with a double base epilayer that is continuously grown.The measured dc common-emitter current gain is 16.8 at IC = 28.6 mA(J C = 183.4 A/cm2),and it increases with the collector current density increasing.The specific on-state resistance(Rsp-on) is32.3mΩ·cm 2 and the open-base breakdown voltage reaches 410 V.The emitter N-type specific contact resistance and N + emitter layer sheet resistance are 1.7×10-3 Ω·cm2 and 150 /,respectively.