Tunable laser Stark-difference spectra of CD3OH

We present Doppler resolution limited spectra of the P(J) and R(J) multiplets for J ≦ 10 of the 10-μm CO stretch band of ¹²CD₃¹⁶OH using a tunable diode laser. Relative frequencies within the multiplets accurate to ±0.0002–0.0005 cm^?1 are obtained, but no absolute frequencies are given. We are able to assign most of the hindered rotation and K substructure in these multiplets. The assignments are based on analyses of Stark-difference spectra combined with the ground-state microwave data and the intensity variations which are expected theoretically. The ground and excited state A, K = 1 asymmetry splitting parameters are measured to be δ₁″ = (8.5450 ± 0.0080) × 10^?3cm^?1 and δ₁′ = (9.7706 ± 0.0080) × 10^?3cm^?1, respectively. The ground-state value agrees well with the microwave results. A rapid-scan system for recording data and a computer-aided technique for calibrating and plotting the spectra are described.     

Absorption of H and D Ly-α radiation by O2 molecules at high temperatures

Absorption cross sections of molecular oxygen were measured at the H and D Ly-α wavelengths (1215.67 and 1215.34 Å) between 800 and 1700°K, the cross sections being given by the equation σ (cm²) = 4.2E-18 exp(-3070/T) (4.2E-18 = 4.2 × 10^-18). The absorption cross section for v = 1 is (9±2)E-19 cm² and that for v = 2 is (7±3)E-18 cm², compared to 1.E-20 cm² for v = 0. Vibrational relaxation times were found to be in agreement with literature data over the range of common temperatures.     

The forced magnetostriction of nickel at 4.2 K

The forced volume magnetostriction of polycrystalline nickel at 4.2 K has been determined with a relative accuracy of 2 × 10^?2. Combining our result with previous data on the forced magnetostriction, we derive for the forced magnetostriction constants: h'₀ = (40 ± 1) × 10^?8T^?1, h'₁ = (-95 ± 2) × 10^?8T^?1, h'₂ = (-19 ± 2) × 10 ^?8T^?1.     

ESR study of vanadyl ion in trisodium citrate pentahydrate

ESR study of VO²⁺ doped trisodium citrate pentahydrate is undertaken at room temperature. The observed spectra are correlated with the available crystal structure data and are fitted to a spin Hamiltonian of orthorhombic symmetry with g_x = 1.998 ± 0.001, g_y = 1.992 ± 0.001, g_z = 1.934 ± 0.001, A_x = (70.0 ± 1) × 10^-4cm^-1, A_y = (66.6 ± 1) × 10^-4cm^-1 and A_z = (175.4 ± 1) × 10^-4cm^-1. The covalency and Fermi contact parameters are evaluated and compared with those of VO²⁺ in other lattices.     

The ground state of molecular hydrogen

The v = 0?0 quadrupole spectrum of H₂ has been recorded using a 0.005-cm^?1 resolution Fourier transform spectrometer. The rotational lines S(1) through S(5) are observable in the spectra, in the region 587 to 1447 cm^?1. The spectral position for S(0) was also obtained from its v = 1-0 ground-state combination difference. The high accuracy of the H₂ measurements has permitted a determination of four rotational constants. These are (in cm^?1) B₀ = 59.33455(6); D₀ = 0.045682(4); H₀ = 4.854(12) × 10^?5; L₀ = ?5.41(12) × 10^?8. The hydrogen line positions will facilitate studies of structure and dynamics in astrophysical objects exhibiting infrared H₂ spectra. The absolute accuracy of frequency calibration over wide spectral ranges was verified using 10-μm CO₂ and 3.39-μm CH₄ laser frequencies. Standard frequencies for 5-μm CO were found to be high by 12 MHz (3.9 × 10^?4 cm^?1).     

Absolute intensity measurements of the CO2 bands 401III←000 and 411III←010

The absolute intensities of the transitions 401_III←000 and 411_III←010 of CO₂ have been measured from spectra obtained under high resolution. Both the vibration-rotation line intensities and the integrated band intensities are reported. The rotationless transition moment of 401_III←000 is deduced and a vibration-rotation interaction factor F(m) = 1+(4.92×10^?4)m+(4.4×10^?7)m² is determined. The values obtained are: S_Band(401_III←000) = (25.54±0.22)×10^?5 cm^?2atm_{(293 K)}^?1, |R₀₀₀^401_III| = (1.87±0.02)×10^?4D, and S_Band(411_III←010) = (1.83±0.13)×10^?5 cm^?2atm_{(293 K)}^?1.     

A monte-carlo/molecular dynamics study of the diffusional recombination kinetics of C(a) + O(a) → CO(g) on Pt(111)

The diffusion constants for C and O adsorbates on Pt(111) surfaces have been calculated with Monte-Carlo/Molecular Dynamics techniques. The diffusion constants are determined to be D_C(T)=(3.4 × 10^?3e^{$\text{?13156}\text{T}$})cm²s^?1 for carbon and D_O(T) = (1.5×10^?3 e^{$\text{?9089}\text{T}$}) cm² s^?1 for oxygen. Using a recently developed diffusion model for surface recombination kinetics an approximate upper bound to the recombination rate constant of C and O on Pt(111) to produce CO_(g) is found to be (9.4×10^?3 e^{$\text{?9089}\text{T}$}) cm² s^?1.     

Shock-tube study of HCN self-broadening and broadening by argon for the P(10) line of the ν1 band at 3 μm

A tunable infrared diode laser was used to measure the fully resolved absorption line shape of the P(10) line in the ν₁ band (10°0–00°0) of HCN for shock-heated mixtures of HCN-Ar at temperatures of 1000, 1500 and 2000 K. The temperature dependence of the collision-broadening coefficients 2γ (cm^-1 atm^-1, FWHM) were inferred for both self-broadening and broadening by argon. For the assumed form 2γ = 2γ₀(T₀/T)ⁿ the exponent n was determined to be 0.63 ± 0.06 with 2γ₀ = 0.11 cm^-1atm^-1 and T₀ = 300 K for argon-broadening in the range 300 < T < 2000 K, and 1.2 ± 0.6 with 2γ₀ = 0.68 cm^-1atm^-1 and T₀ = 1000 K for self-broadening in the range 1000 < T < 2000 K.     

The absorption spectrum of CO2 around 7740 cm-1

Absolute intensities of the vibration-rotation lines of the CO₂ 401_II←000 band 7734 cm^-1 are measured under high-resolution, low-pressure conditions by use of a White-type 25-m base-path, absorption cell together with a 5-m Czerny-Turner spectrometer. The total band intensity S_B, the purely vibrational transition moment

, and the vibration-rotation interaction constant ζ are calculated from the intensity measurements. The values obtained for these parameters are S_B(401_II) = (7.06±0.07) × 10^-5 cm^-2 atm^-1_293°K,

= (3.08±0.03)×10^-5 debye, and ζ = (2.5±0.5)×10^-4. The intensity of the associated “hot band” 411_II←010 is also determined and found to be S_B(411_II←010) = (0.53±0.02)×10^-5 cm^-2 atm^-1_293°K.     

Temperature-dependent light scattering from magnetic excitons in TlCoF3

Raman spectra of antiferromagnetic thallium cobaltous fluoride have been obtained with 4579A argon ion laser excitation at temperatures from 4°K to T_N = 94 ± 2°K. The features observed consist of six Co²⁺ excitons ranging in energy from 325 to 1070 cm^-1, at two-magnon peak with low-temperature energy of 315 cm^-1, and a one-magnon feature whose 4°K energy is 37 cm^-1. The energy and linewidth of the one-magnon scattering has been measured from 4°K to about 0.8 T_N; it is found that the magnon becomes critically damped at about 0.8 T_N, in good agreement with our previous observations on RbCoF₃. The Co²⁺ excitons observed at 325, 380, 410, 730 (weak), 960, and 1070 cm^-1 agree in energy quite well with the KCoF₃ levels calculated by Buyers, Holden et al. as 340, 400, 467, 767, 967 and 1050 cm^-1.     

The analysis of symmetric rotor Raman spectra: The pure rotational spectrum of 11BF3

The pure rotational Raman spectrum of ¹¹BF₃ has been photographed. Great care was taken in the analysis to consider all the unresolved components under each observed Raman line profile. If this is ignored, systematic errors result. The final set of molecular constants obtained was B₀ = 0.34502(±3 × 10^?5)cm^?1, D_J = 4.38(±0.10) × 10^?7cm^?1, and D_JK = ?9.1(±1.0) × 10^?7cm^?1.     

Far-infrared reflection spectra of HgSe

Reflectivity of HgSe (N = 2.0 × 10¹⁸-4.2 × 10¹⁷ cm^-3) was measured in the spectral region from 2–100 μm at temperatures between 95 and 300 K. The frequency of the transverse optical phonon ω_t = 132 ± 2 cm^-1 was determined from Kramers-Kronig analysis. The ω+ mode of the plasmon-LO phonon coupled modes is shown to depend anomalously on temperature. Two extra bands of unknown origin were also observed at about 110 and 120 cm^-1.     

Pressure broadening of the oxygen λ5577 Å line by rare gas

We report on measurements of collision broadening of the electric quadrupole transition λ5577.35 Å in oxygen by argon, krypton and xenon. The broadening constant (linewidth added per unit atom density) was found to be: (4.3 ± 2.3) × 10^-21 cm^-1 atom^-1 cm³ for argon (reported earlier), (8.0 ± 1.7) × 10^-21 cm^-1 atom^-1 cm³ for krypton, and (10.0 ± 2.0) × 10^-21 cm^-1 atom^-1 cm³ for xenon. We discuss some experimental problems associated with these measurements.     

Improving the mobility of CuPc OFETs by varying the preparation conditions

In this work, three different preparation conditions were used for testing the performance of p-conducting copper phthalocyanine (CuPc) organic field-effect transistors (OFETs). The charge carrier mobility (μ _sat=(1.5±0.6)×10^?3 cm²/V?s) of the CuPc OFETs with the CuPc film deposited while keeping the substrate at room temperature could be improved when the gate dielectric was modified by a self-assembled monolayer of n-octadecyltrichlorosilane (μ _sat=(3.8±0.4)×10^?3 cm²/V?s) or when elevated temperatures were applied to the substrate (T _S,av=127 ^°C) during the deposition of the organic film (μ _sat=(6.5±0.8)×10^?3 cm²/V?s). For the latter case, the dependence of the mobility and threshold voltage with increasing thickness of the organic film was tested—above 13 nm film thickness, no further significant increase of the hole mobility or change in the threshold voltage could be observed. The environmental stability of the OFETs was checked by performing ex situ measurements immediately as the sample was exposed to atmosphere and after 40 days of exposure. The effect of the different preparation conditions on the morphology of the organic films prepared in this work is also discussed in this context.     

Proton spin-lattice relaxation in iron fluosilicate

Proton T₁ of FeSiF₆·6H₂O is proportional to exp (Δ/kT)at liquid helium temperatures, with Δ ≈ D - 3E. We find the crystal field splitting of the Fe²⁺ ion in this salt to be D = (12.2 ± 1.0) cm^-1 using E = 0.54 cm^-1.     

Shock-tube determination of absorption cross sections and A2Δ − X2Π band transition moments of SiH

The overall absorption cross sections and electronic transition moments of the A²Δ ? X²Π band system of SiH have been determined by using an absorption technique with a shock tube at temperatures of 2600–3800 K over the wavelengths of 150–650 nm. Absorption cross sections are shown to be dominated by continua. The possible contributions to the overall cross sections by a low-lying ⁴Σ^- and a high-lying ⁴Σ^- state are discussed. At 200, 228, 340, 405, and 550 nm, the continuum cross sections are (2.9±1.0)×10^-17, (2.0±0.5)×10^-17, (3.2±0.6)×10^-18, (3.8±0.6)×10^-18, and (1.8±0.8)×^-18cm², respectively. The overall emission intensity and the Si+H→SiH+hv radiative recombination rate are (6.7± 2.3)×10^-35(3500/T)^0.7(Si)(H) watt-cm^-3 and (1.3±0.4)×10^-17(3500/T)^1.1(Si)(H) cm^-3-s^-1, respectively. The A ? X transition moments are 0.12±0.04a.u. for the (0, 0) and (1, 1) bands. The intensity of each branch in the A ? X (0, 0) band follows approximately the prediction based on the Hönl-London factors of Kovacs. The data are applied to the study of the flow field around a spacecraft entering the Jovian atmosphere.     

ESR study of vanadyl ion in tripotassium citrate

ESR spectra of VO²⁺ doped tripotassium citrate are recorded at room temperature. The observed spectra are fitted to a spin Hamiltonian of orthorhombic symmetry with g_x = 2.001 ± 0.001, g_y = 1.997 ± 0.001, g_z = 1.945 ± 0.001, A_x = (49.0 ± 1) × 10⁻⁴ cm⁻¹, A_y = (66.8 ± 1) × 10⁻⁴ cm⁻¹ and A_z = (168.4 ± 1) × 10⁻⁴ cm⁻¹. The covalency and Fermi contact terms are evaluated and compared with those of other lattices.     

Elastic constants of solid krypton at T = 77 K determined by inelastic neutron scattering

Long-wavelength acoustic phonons have been studied for each of the [ζ00]T, [ζ00]L, [ζζ0]L and [ζζ0]T₁ branches in solid Kr at T = 77 K by means of inelastic neutron scattering utilizing ‘cold neutrons’ as they are available in the long-wave length tail of the pile spectrum. The raw data have been corrected for resolution effects taking into account the curvature of the dispersion surface and variation of mode eigenvectors. It has turned out, that this yields appreciable shifts of the raw data. The results of our experiment give c₁₁ = 4·25 ± 0·10, c₄₄ = 2·04 ± 0·03, c₁₂ = 2·82 ± 0·12 and a value for B = (c₁₁ + 2c₁₂)/3 = 3·30 ± 0·09 × 10¹⁰ dyne/cm². Available thermodynamic data for Kr gives a derived value for B^ad = 2·58 ± 0·06 × 10¹⁰ dyne/cm² indicating a large difference between zero sound and first sound in solid Kr at high temperatures.     

Microwave determination of the conformation and dipole moment of 1,3-difluoroacetone

The microwave spectra of the ground state and several low-lying vibrational modes of 1,3-difluoroacetone have been assigned and analyzed. The assigned form has a molecular conformation in which one fluorine atom lies cis and the other trans to the oxygen atom. The rotational constants of the ground state species were determined using a centrifugal distortion analysis: A = 6024.843 ± 0.006 MHz, B = 2454.414 ± 0.001 MHz, C = 1783.897 ± 0.001 MHz. The molecular dipole moment components of the ground state species lie along the a and b principal axes with μ_a = 2.38 ± 0.03 D, μ_b = 0.89 ± 0.03 D, and μ_T = 2.54 ± 0.03 D. Comparative intensity measurements with OCS microwave lines indicate that the assigned form constitutes only 20% to 30% of the total gas mixture, the remainder presumably consisting of one or more other conformers, perhaps the gauche-gauche form. The lowest vibrational frequency (82 ± 12 cm^?1) is attributed to the trans-CH₂F torsion, while the next-higher vibrational frequency (127 ± 15 cm^?1) is believed to be the cis-torsion. A low-frequency in-plane bending motion is found at 285 ± 25 cm^?1.