High resolution FTIR spectra of AsD3 in the 20-1000 cm−1 region. The ground, 98, v2 = 1 and v4 = 1 states

The pure rotational spectrum of the near-spherical oblate symmetric top AsD₃ has been recorded in the 20–120cm^?′ region with a resolution of 2.3 × 10^?3 m^?1 employing an FT interferometer. Rotational transitions with 5 ? J ? 29 and 0 ? X ? 25 of the ground state (GS) and the v₂ = 1 and v₄ = 1 excited states have been assigned. Splittings were observed for the GS, 98, K = 3 and 6 levels, the K = 3 levels of v₂ and the kl = ?2, 1, 4 and 7 levels of v₄. Furthermore the x,y Coriolis coupled v₂ and v₄ bands, v ⁰ ₂ = 654.4149cm^?1, and v ⁰ ₄ = 714.3399 cm^?1, have been examined with a resolution of 2.4 × 10^?3 cm^?1, and ca. 2500 allowed and 336 ‘forbidden’ lines with J′_max = 31 and K′_max = 28 have been assigned. Appropriately weighted GS data comprising FIR lines, allowed and ‘forbidden’ (up to ΔK = ±6) GS combination differences, mmw data, and ΔJ = 0, ΔK = ±1 distortion moment transitions were fitted together, and GS parameters complete through H parameters have been determined. Two different reductions of the Hamiltonian, either with ΔK = ±6 (h₃) or ΔK = ±3 (ε) off-diagonal elements, have been employed. Equivalence of these reductions up to J = 22 was established while for J > 22 the ε reduction is superior. The v₂ and v₄ data have been fitted with two equivalent models based on different reductions of the rovibrational Hamiltonian. In addition to the dominating x,y Coriolis resonance, ζ ^y ₂₄ 0.520, Δ(k ? l) = ±3 and ±6 interactions are important and were accounted for by the models. The transition moment ratio |M₄: M₂| =0.75 has been determined, with a positive sign of the product M ₂ζ ^y ₂₄ M ₄. An improved r₀ structure, r₀(AsD) = 1.51753 Å and α₀(DAsD) = 92.000°, has been determined.     

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 rotational levels of the ground vibrational state of formaldehyde

A variational procedure for rovibrational energy levels and wavefunctions of centrally connected tetra-atomic molecules is extended to include high rotational states, and in particular, J ? 10 levels for the vibrational ground state of formaldehyde. It is very important to do this because it has made possible the calculation of the usual rotational spectroscopic constants which correspond to the forcefield and geometry. A direct comparison with the ‘observed’ spectroscopic constants is therefore possible. The geometry and forcefield are refined against 65 J = 0 levels of H₂CO, 6 J = 0 levels of D₂CO, 42 J = 1, 70 J = 2 and 98 J = 3 levels of the ground and fundamentals of H₂CO and D₂CO, using an iterative scheme. The mean absolute error of the J = 0 levels is 1·10 cm^?1 and that for J ≠ 0 is 0·005 cm^?1, and the predicted geometry is CH = 1·10064 Å, CO = 1·20296 Å and HCO = 121·648°. Finally, the rotational constants A, B, and C for the ground state are 281956, 38846 and 34003 MHz, compared with the observed values 281971, 38836, and 34002 MHz. The centrifugal distortion constants Δ_J , Δ_JK , Δ_K and δ_J , are 77, 1275, 18113 and 11 kHz compared with 75, 1291, 19422 and 10 kHz. These results underline the accuracy of the new quartic forcefield.     

The ν2 Raman band of CD4

The rather weak ν₂ Raman band of CD₄ has been recorded with a resolution of about 0·45 cm^-1. The data have been analysed in two ways: (i) treating ν₂ as an isolated band, and (ii) analysing the ν₂ and ν₄ bands together by a simultaneous diagonalization of the v ₂=1 and v ₄=1 states coupled by the Bζ_2,4 Coriolis interaction term. Although the former treatment is satisfactory for low J values, the explicit inclusion of the Coriolis coupling is necessary to reproduce the observed spectrum for all J values.     

High resolution study of the v 7 + v 8 band of ethylene (C2H4) at 1889 cm-1

The v ₇ + v ₈ A-type band of C₂H₄ has been recorded between 1932 and 1847 cm^-1 with a resolution of 0·06 cm^-1. The transitions with K _-1 ? 8> and J ? 2>5 have been assigned. Although slight Coriolis resonances perturb the band, the analysis has been made easy through the use of an elaborate set of asymmetric top computer programmes. The band centre and a set of upper state constants have been obtained. With these constants, 288 observed upper state energy levels have been fitted with a standard deviation of 0·021 cm^-1.

Using very simple expressions, we have predicted all the resonance effects perturbing the levels of ethylene near 2000 cm^-1. This led us to the identification of the v ₄ + v ₈ and v ₈ + v ₁₀ combination bands in low resolution spectra.     

Far infrared spectrum and spectroscopic constants of AsH3 in the ground state

The far ir spectrum of arsine, AsH₃, was recorded in the range 25–100 cm^?1 with a resolution of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0 rotational transitions were measured and assigned up to J″ = 12. These transitions, together with the presently available microwave and submillimeter-wave data and ground state combination differences, were analyzed on the basis of a rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The derived ground state molecular parameters reproduced the transition frequencies of both allowed and “perturbation allowed” transitions within the accuracy of the measurements. The equilibrium structure was determined for the AsH₃ molecule.     

The ν6 infrared band of 1-phosphapropyne CH3CP

The Fourier transform infrared spectrum of 1-phosphapropyne CH₃P was recorded in the region 1250–1550 cm⁻¹ at resolutions of 0.12 and 0.01 cm⁻¹. The ν₆^±1 band, centered at 1437.4748(29) cm⁻¹, was analyzed by taking account of a strong Coriolis interaction with ν₃ together with further Coriolis and Fermi interactions with ν₄ + 2ν₈^±2. On the basis of a Loomis-Wood diagram, 818 observed transitions with J ≤ 40 and K ≤ 9 have been assigned. A set of molecular constants was determined from a fit of the transitions with a rms error of 0.0037 cm⁻¹. A minor localized perturbation was also observed in the ^RR₂ branch and explained by a Coriolis interaction between ν₆^±1 and 2ν₄.     

Intensity measurements in the v4-fundamental of methane

The absolute intensities of all the J-multiplets between R(13) at 1375cm^-1 and P(12) at 1225 cm^-1, in the v₄-fundamental of ¹²CH₄, have been measured at 300°K. Our values are consistent with published band-intensity measurements and also with the theoretical line strength tabulation by Fox. Spectral transmittance computation using a Lorentz line shape with a hydrogen-broadened half-width of 0.075 cm^-1 atm^-1 at 300°K for all the lines in the band is in excellent agreement with our experimental data measured with a spectral resolution of 0.2 cm^-1. Our best estimate for the absolute intensity of the band is 145±8 cm^-2 atm^-1 at STP.     

Tunable laser study of the ν10 + ν11 band of cyclopropane

Diode laser measurements of the ν₁₀ + ν₁₁ (l_tot = ±2) perpendicular band of cyclopropane have led to the assignments of roughly 600 lines in the 1880–1920-cm^?1 region. Most of the spectra were recorded and stored in digital form using a rapid-scan mode of operating the laser. These spectra were calibrated, with the aid of a computer, by reference to the R lines of the ν₁ + ν₂ band of N₂O. The ground state constants we obtained are (in cm^?1) B = 0.670240 ± 2.4 × 10^?5, D_J = (1.090 ± 0.054) × 10^?6, D_JK = (?1.29 ± 0.19) × 10^?6, D_K = (0.2 ± 1.1) × 10^?6. The excited state levels are perturbed at large J values, presumably by Coriolis couplings between the active E′(l_tot = ±2) and the inactive A′(l_tot = 0) states. Effective values for the excited state constants were obtained by considering only the J < 15 levels. The A₁-A₂ splittings in the K′ = 1 excited states were observed to vary as q_effJ(J + 1), with q_eff = (2.17 ± 0.17) × 10^?4 cm^?1.     

Intensity measurements,self-broadening coefficients,and rotational intensity distribution for lines of the oxygen B band at 6880 Å

Quantitative measurements of intensities and half-widths were made for individual rotational lines of the atmospheric oxygen B band. The total band intensity, as derived from the line intensity measurements, is 40·8±0·6 cm^?1km^?1atm^?1 STP. As had been previously found in this laboratory for the oxygen A band, the relative line intensities conform closely to the rotational distribution calculated by either Schlapp or by Watson. The line half-widths at half-intensity were determined for oxygen self-broadening for the ${}^{\mathrm{P}}\text{Q}$ and ${}^{\mathrm{P}}\text{P}$ branch lines and for a few ${}^{\mathrm{R}}\text{Q}$ and ${}^{\mathrm{R}}\text{R}$ branch lines near the band origin, and were found to vary from 0·064 cm^?1atm^?1 at J′ = 1 to 0·042 cm^?1atm^?1 at J′ = 25.     

Far-infrared rotational spectra of some freons; chlorotrifluoromethane,dichlorodifluoromethane, and trichlorofluoromethane

The far-infrared rotational spectra of chlorotrifluoromethane, dichlorodifluoromethane, and trichlorofluoromethane have been observed with an interferometric (Fourier transform) spectrometer in the region 10–40 cm^?1 at a resolution of 0.07 cm^?1. CCl₂F₂ exhibits a continuum spectrum at this resolution, but symmetric top rotational fine structure is observed for CClF₃ and CCl₃F. Isotope splitting is also observed in CClF₃, and analysis yields the rotational constants for C³⁵ClF₃ of B₀ = 0.11112 cm^?1, D_J = 1.6 × 10^?8cm^?1; and for C³⁷ClF₃, B₀ = 0.10835 cm^?1, D_J = 1.5 · 10^?8cm^?1. Isotopic shifts can be allowed for in CCl₃F to yield constants for C³⁵Cl₃F of B₀ = 0.0821 cm^?1, D_J = 1 × 10^?8cm^?1. These values are all in agreement with those deduced from microwave studies of the low J transitions apart from B₀ for C³⁵ClF₃, where the difference is outside the expected experimental error.     

Diode laser spectra of the ν2 band of H212CO and H213CO

The Q-branches of the ν₂ (CO stretch) band of H₂¹²CO and H₂¹³CO have been studied in high resolution using an infrared diode laser. Accurate upper state constants, including A, B, C, Δ_J, Δ_JK, Δ_K, and H_K, were determined from an analysis of the data for 97 lines of H₂¹²CO and 79 lines and H₂¹³CO and compared with previous reported values. Band centers were also determined and reported as 1746.009 ± 0.002 cm^?1 for H₂¹²CO and 1707.981 ± 0.002 cm^?1 for H₂¹³CO.     

Inversion-rotation spectrum and spectroscopic parameters of 14ND3 in the ground state

The far-infrared spectrum of ¹⁴ND₃ has been recorded in the region between 30 and 220 cm^?1 at a resolution, before deconvolution, of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0, a ← s and s ← a inversion-rotation transitions have been measured and assigned up to J″ = 19. These transitions, the pure inversion-microwave transitions and ground-state combination differences from the analysis of the ν₂ and ν₄ bands have been fitted simultaneously to an inversion-rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The ground-state spectroscopic parameters obtained in this way reproduce the transition frequencies within the accuracy of the measurements.     

Analysis of the ν 3, ν 6, ν7 + ν 8 Fermi and Coriolis interacting band system in methyl cyanide

A reinvestigation of the Fermi and Coriolis interacting band system ν ₃, ν ₆, ν ₇ + ν ₈ of methyl cyanide has been performed with a resolution better than 0·3 cm^-1. The observed J structure in some of the K sub-bands enables an unambiguous numbering of the sub-band Q branches to be made. The resulting assignment, which differs from Amat and Nielsen's previous assignment, is used to re-analyse the band system. A band contour has been calculated by computer simulation, including the effects of both the Fermi resonance of ν ₆ with ν ₇ + ν ₈ and the Coriolis resonance of ν ₆ with ν ₃; both the frequency and intensity perturbations which result have been accurately reproduced. The molecular parameters obtained from our analysis are summarized in table 2.     

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.     

The ν2 and ν4 bands of AsH3

The infrared absorption of arsine, AsH₃, between 750 and 1200 cm^?1 has been recorded at a resolution of 0.006 cm^?1. Altogether 2419 transitions, including nearly 700 “perturbation allowed” transitions with Δ∥k ? l∥ = ±3, ±6, and ±9, have been assigned to the ν₂(A₁) and ν₄(E) bands. Splitting of the transitions for K″ = 3, 6, and 9 was also observed. To fit the rotational pattern of the v₂ = 1 and v₄ = 1 vibrational states up to J = 21, all the experimental data were analyzed simultaneously on the basis of a rovibrational Hamiltonian which took into account the Coriolis interaction between ν₂ and ν₄ and also included several essential resonances within them. The derived set of 38 significant spectroscopic parameters reproduced the 2328 transition wavenumbers retained in the final fit within the accuracy of the experimental measurements.     

Infrared transitions of C2D6 from v 4 to the interacting system v 4+ v 6, v 4+ v8, v 3+ 2v 4: rotational analysis,and torsional splitting in the v 3+ 2v 4 and v 3+ v 4 states

The hot infrared transitions of C₂D₆ from the υ₄(A_1u ) to the υ₄ + υ₆(A_2g ) and υ₄ + υ₈(E _g ) vibrational states, observed from 960 to 1180 cm^?1, have been rotationally analysed on a high-resolution Fourier transform spectrum (full width at half-maximum about 0·0030 cm^?1). The vibration-rotation interactions affecting the upper vibrational states are very similar to those of the corresponding cold system. A strong x,y Coriolis interaction between υ₄ + υ₆ and υ₄ + υ₈, with K-level crossing, generates large displacements of the rotational components of both vibrational states, tuning them to additional local resonances in several spectral regions. Thus l resonances with Δl = ±2, Δk = ±1 occur within υ₄ + υ₈. A x,y Coriolis-type resonance between υ₄ + υ₈(?l,K ? 1) and υ₃ + 2υ₄(K) occurs at K = 11,12,13, and a further coupling of υ₄ + υ₈(+l,K + 1) and υ₃ + 2υ₄(K + 3) is most effective at K = 11 and 12. These resonances induce torsional splittings on the perturbed levels of υ₄ + υ₈ and allow us to determine the torsional splittings in the υ₃ + 2υ₄ state. The vibration-rotation constants of υ₄ + υ₆, υ₄ + υ₈ and υ₃ + 2υ₄, several interaction parameters and the torsional splitting of υ₃ + 2υ₄ have been determined by least-squares fit of 1391 observed transition wavenumbers, with an overall standard deviation σ = 0·75 × 10^?3 cm^?1. The vibrational wavenumbers found for the four torsional components of (υ₃ + 2υ₄)? υ₄ are υ(E_3d) = 1040·961 82(809)cm^?1, υ(A_3d) = 1041·218 27(865)cm^?1, υ(E_3s) = 1041·225 23(662)cm^?1 and υ(A_1s) = 1041·407 77(633)cm^?1. These are anomalous for both the order of the torsional components and the magnitudes of their separations. We believe that this is mainly due to the interactions of υ₃ + 2υ₄ with the torsional manifolds with υ₃ = 0 and υ₃ = 2, through the vibration-torsion Hamiltonian term (?V ₆/?q ₃)q ₃cos (6γ)]/2. The further observation of a few doublets of υ₈ and υ₃ + υ₄ at resonance provides information on the torsional splitting of the latter state.     

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.     

The perpendicular fundamental v5 of chloroform 12CH35Cl3: high resolution infrared study of the v5 band together with the millimetre-wave rotational spectrum

The infrared spectrum of the perpendicular fundamental v₅ of chloroform around 776 cm^?1 has been studied by applying two high resolution methods. A short range from the central part of the spectrum was measured with a diode laser by using a cold jet sample including chloroform in natural isotopic abundancies. More than 100 rotational lines of ¹²CH³⁵Cl₃ could be assigned. The whole band region was measured by a Fourier transform spectrometer at a resolution of 0.0010cm^?1. In this case an isotopically pure sample of ¹²CH³⁵Cl₃ was used. Starting from the results of the diode laser investigation more than 2000 lines could be assigned with J_max = 91 and K_max = 58. In addition to the infrared spectra, millimetre-wave lines also were measured. A total of 58 lines corresponding to J values 22, 23 and 35 at the excited vibration state v₅ = 1 were assigned and analysed. All the data from three different spectra were simultaneously fitted and, for example, the results v₀ = 775.961 50(3) cm^?1, 98, B₅-B₀ = ?0.180171(22) × 10^?3cm^?1, C₅ ? C₀ = ?0.170 57(15) × 10^?3cm^?1, and (Cζ)₅ = 0.047 5294(11) cm^?1 were obtained.     

Millimeter wave dispersion in ethyl chloride

Dispersion of millimeter waves due to ethyl chloride in the range ν=1·34 cm^?1 to 1·44 cm^?1 is computed by means of quantum mechanical formulas. It is found that dispersion is due to (i) contribution of sixR branch rotational lines in the region considered, (ii) contribution ofR branch lines away from the region and (iii) the contribution ofQ branch lines at zero wavenumber. The maximum variation in the susceptibility is 1·9 × 10^?5 and occurs at ν=1·39 cm^?1 due to combined contribution of transitions at 1·3878 cm^?1, 1·3902 cm^?1 and 1·3927 cm^?1.