Coherent Stokes and anti-Stokes Raman spectra of the ν1 (A1) and ν2 (E) bands of SF6 and UF6

Coherent Stokes and anti-Stokes Raman scattering are used to study the ν₁ and ν₂ spectral band profiles of UF₆ and SF₆. Most of the observed SF₆ “hot” bands are assigned, leading to evaluations of the anharmonicity constants X_ij: X₁₂ = ?(2.80 ± 0.30) cm^?1, X₁₄ = ?(1.00 ± 0.15) cm^?1, X₁₅ = ?(1.00 ± 0.15) cm^?1. For UF₆, a tentative assignment of the “hot” bands is made: X₁₂ = ?(1.80 ± 0.30) cm^?1, X₁₃ = ?(1.60 ± 0.30) cm^?1, X₁₄ = ?(0.20 ± 0.10) cm^?1, X₁₅ = ?(0.25 ± 0.10) cm^?1, and X₁₆ = ?(0.10 ± 0.05) cm^?1. Parameters such as the vibration-rotation coupling constants are determined. For SF₆: α = (7 ± 2) × 10^?5 cm^?1 for the ν₂ band and α = ?(1.02 ± 0.01) 10^?4 cm^?1 for the ν₁ band. The calculated spectral profiles of the coherent Stokes or anti-Stokes spectra, which are in good agreement with experimental results, give values for the resonant and nonresonant parts of the susceptibility in both molecules. They also show, in some cases, the influence of neighboring combination bands.     

Absolute frequency measurement of a lamb-dip stabilised water vapour laser oscillating at 10.7 THz (28 μm)

A 10.7 THz (28μm) water vapour laser has been stabilised to the Lamb dip. The centre frequency has been measured using an 0.89 THz (337 μm) hydrogen cyanide laser as a transfer oscillator and found to be 10718 068.71 ± 0.03 MHz (ie ± 3 × 10^?9) over a wide range of operating conditions.     

Drift mobility measurements in melt-grown baryum titanate

Drift mobility measurements in melt-grown BaTiO₃ single crystal have been performed using the Spear method. The mobility of (3 ± 1) × 10^?3 cm²V^?1 sec^?1 at room temperature is found to be thermally activated, with an activation energy of 0.15 ± 0.04 eV. Two interpretations are investigated to explain these results: trapping effects due to oxygen vacancies or small polaron hopping.     

Van der Waals broadening of argon absorption lines

Van der Waals broadening coefficients for Ar absorption lines have been measured using the resonant Faraday effect. These coefficients have the values of 2·9 ± 0·8, 2·4 ± 0·3, 1·9 ± 0·2 (in units of 10^?20 cm^?1 ?cm^?3) for the lines 6965 Å, 7067 Å, 7635 Å and 8115 Å, respectively, respectively. The measured coefficients are in reasonable agreement with measurements carried out on Ar emission lines and with theoretical calculations.     

Line strengths and self-broadened linewidths of N2O in the 2-μm region: 2400-0000 and 0112-0000 transitions

The strenghths and self-broadened linewidths of the parallel 24⁰0-00⁰0 and perpendicular 01¹2-00⁰0 bands of N₂O have been measured with a precision better than 3%, using a deconvolution procedure. For both transitions, the coefficient of the vibration-rotation interaction polynomial, the values of the rotationless dipolar transition moment, and the band intensity have been calculated from the line strengths. For the total intensity the values found are S_00⁰0²⁴⁰⁰ = (1.325 ± 0.021) × 10^?2 cm^?2·atm^?1 and S_00⁰0⁰¹¹² = (1.209 ± 0.018) × 10^?2 cm^?2·atm^?1.     

Observations on the electronic spectrum of gaseous FeO

About 400 lines are assigned to FeO emission bands in the region 5580 to 6265 Å. The lower state of all the bands analyzed is identified as the ground state of the molecule, for the value of the lower-state vibration frequency (ω_e = 880.61 ± 0.02 cm^?1) is in excellent agreement with that observed in low-temperature matrix isolation, itself confirmed by isotopic substitution. This state is also observed as the lower state in laser-induced fluorescence. However, 880 cm^?1 is significantly smaller than the value found in laser photodetachment studies of FeO^? (970 ± 60 cm^?1). The rotational analysis is consistent with a parallel transition, ΔΛ = 0, but the value of Λ is not determined. According to theoretical calculations, the orange bands most probably arise from a ⁵Σ-⁵Σ transition. There is at least one nearby excited state, for all analyzed upper levels are perturbed.     

Line strengths,spin-splittings,and forbidden transitions in the (101) band of 14N16O2

Measurements of line strengths in the (101) and (111)-(010) bands of ¹⁴N¹⁶O₂ have been made at a resolution of 0.02 cm^?1 in the region 2863 to 2934 cm^?1. The strength data in the (101) band were analyzed to determine a vibrational band strength and coefficients of the F factor. Each subband for K_?1 ≤ 9 was analyzed separately and all the F-factor coefficients in terms of the rotational quantum number, N, were found to be too small to be of significance. However, F was found to be dependent on K_?1 and the experimentally determined subband strengths were least-squares fitted to the expression S_v⁰·F, where S_v⁰ = 68.3 cm^?2 atm^?1 at 296 K and F = 1 + (2.899 × 10^?3)K_?1 + (4.08 × 10^?3)K_?1² ? (2.34 × 10^?4)K_?1³. The integrated strengths for the (101) and (111)-(010) bands were found to be 70.9 ± 2.3 and 2.7 ± 0.3 cm^?2 atm^?1 at 296 K, respectively. Also included in this study are measurements of line center positions in the two bands and spin-splittings in the (101) band. Recent frequency measurements of lines with K_?1 ≤ 8 in the (101) band have been made at a resolution of 0.0033 cm^?1 by V. Dana and J. P. Maillard (J. Mol. Spectrosc.71, 1–4) (1978)) for the region above 2889 cm^?1 and our values are in excellent agreement with theirs. Separations of the split lines measured in this work (K_?1 ≤ 10) agree well with calculated values using expressions which include the η_aaaaK_?1⁴ term with η′_aaaa = ?1.70 ± 0.15 × 10^?4 cm^?1 as derived for the (101) state. Three forbidden (ΔN ≠ ΔJ, ΔK_?1 = 0) transitions in the (101) band were observed with their identifications based on the agreement between measured and calculated line positions and strengths.     

Abstracts

Abstract

Isothermal annealing of amorphous Si and Ge has been performed by picosecond pulsed laser irradiation of free-standing films. It is found that the laser induced nucleation rate is about 10²¹-5.10²² cm^?3 s^?1 (Si) and 10²³-10²⁵ cm^?3 s^?1 (Ge) near the melting point. Arrhenius plots of the nucleation rate show that nucleation is thermally activated with an activation energy of about ΔE = 1.8 ± 0.1 eV (Ge) and ΔE = 2.47 ± 0.15 eV (Si).     

Thermochemical properties of small open-shell systems: experimental and high-level ab initio results for NH2 and

The first adiabatic ionization energy and the first singlet–triplet splitting of the amidogen radical (NH₂) have been determined by high-level ab initio quantum chemistry based on the coupled-cluster approach (90?041 and 10?319?cm^?1, respectively) and by high-resolution pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectroscopy (90 083.8 ± 1.0 and 10 222.0 ± 1.3?cm^?1, respectively). A comparison between the theoretical and experimental values demonstrates the predictive powers of high-level ab initio theory in the derivation of the thermochemical properties of small molecular systems. The absolute accuracy of better than 100?cm^?1 alleviates the experimental search for the relevant spectral features.     

A far-infrared bolometric observation of the pinned charge-density wave in TTF-TCNQ

The polarized bolometric signal between 5 and 50 cm^?1 from a TTF-TCNQ single crystal near 10 K has been successfully fitted to a Lorentzian oscillator of natural frequency 3.4 ± 0.6 cm^?1 and a damping of 0.05 ± 0.03 cm^?1. This is presumably the phase mode of the pinned charge-density wave, with interchain Coulomb interaction probably being responsible for the pinning. The low damping is thought to be due to two-phonon “difference” processes, which are also thought to be responsible for a temperature-dependent feature at 25 cm^?1. No dependence of the pinned-mode frequency on electric field could be detected.     

LCGTO-Xα model cluster study for the chemisorption of CO on twofold sites of Ni surfaces

The cluster Ni₂CO is studied as a simplified model for the chemisorption of CO on twofold bridging sites of transition metal surfaces. Using the LCGTO-Xα method we have calculated the potential energy surface for the totally symmetric stretching motion keeping the NiNi distance fixed at the bulk value. The minimum energy is found at a NiC distance of 1.72 Å and a CO bond length of 1.19 Å. The vibrational frequency for the CO bond (1850 cm^?1) shows reasonable agreement with EELS data (1810, 1870 cm^?1), whereas the (Ni₂)C frequency of 495 cm^?1 is remarkably higher than the experimental values (380, 400 cm^?1) indicating an overestimation of the chemisorption bond strength in this simple cluster model. The bonding between CO and Ni is analyzed using orbital correlations, ionization energies and Mulliken population analysis. Important bonding contributions from π backdonation are identified while the a₁orbital manifold exhibits strong antibonding effects.     

The ground-state rotational constants of germane

The ground-state rotational constants B₀, D₀, and H₀ have been determined for GeH₄ from the analysis of ground-state combination differences in the infrared spectra of isotopically enriched ⁷⁰GeH₄, ⁷²GeH₄, and ⁷⁴GeH₄. The spectra were recorded at 0.06-cm^?1 resolution and about 0.005-cm^?1 precision for unblended lines. Suitable combination differences were found in both the ν₂ and the ν₄ infrared bands. The ground-state constants were assumed to be invariant to isotopic substitution at Ge, and the tensor distortion constants were held fixed at their microwave values. The results obtained are: B₀ = 2.69587 ± 0.00007 cm^?1, D₀ = (3.34 ± 0.03) × 10^?5 cm^?1, H₀ = (1.3 ± 0.5) × 10^?9 cm^?1.     

Messung der Wirkungsquerschnitte für die Linienverbreiterung von Hochfrequenzübergängen im 63 P 2-Zustand des Quecksilbers durch Stöße mit Edelgasatomen

The linewidth of high frequency transitions between Zeeman-levels of the metastable 6³ P ₂-state of mercury is measured as function of the pressure of various noble gases. The measurements are made for all noble gases in the pressure range from 10^?3 to about 2 · 10^?2 Torr. The cross sections for linebroadening due to atomic collisions are derived from the pressure dependence of the linewidth. These cross sections σ were found to be (71 ± 10) · 10^?16 cm² for He, (82 ± 10) · 10^?16 cm² for Ne, (153± 12) × 10^?16 cm² for Ar, (204±28) · 10¹⁶ cm² for Kr and (291 ± 41) · 10^?16 cm² for Xe.     

A high resolution FTIR spectroscopic study of the hydrogen-bonded heterodimer H3N−HCN

The spectrum of the symmetric top, hydrogen-bonded heterodimer H₃N?HCN has been recorded between 2900 and 3200cm^?1 using a high resolution FTIR spectrometer. The more intense bands are associated with the ν₂ (H?CN stretch) vibration and include hot bands associated with the low frequency modes ν₅, ν₂ and ν₁₀. Weaker difference bands of the type ν₂+(n?1) ν5?nν₅ are also observed. Analysis of the bands yields values for the band origins: ν2/0=3110·5±0·2cm^?1 and ν5/0=140±5cm^?1 and the anharmonicity constants: x _2,10=12·7±0·5cm^?1, x _2,9≈x _2,5=23±3cm^?1 and x _5,10=?5±2cm^?1. The lifetime in ν₂ with respect to vibrational predissociation, estimated from the width of the sharpest observed feature, is 100?200 ps but there is some indication that this lifetime may decrease at high J.     

Dämpfung von Hyperschall in dünnen Silberschichten bei 9 GHz

The attenuation of longitudinal hypersonic waves (8.4–10.0 GHz) in thin polycrystalline silver films has been measured in the temperature range from 4 to 26 ?K. The silver films with thicknesses between 0.2 and 3.0 Μ. were evaporated on the optically flat polished end surface of a cylindrical quartz transducer. The measured value of the attenuation coefficient α=1.5·10⁴ dB cm^?1 is much higher than the theoretically predicted value due to electron-phonon interaction. Furthermore the measured value α is independent of temperature and increases with the square of frequency. Presumably this attenuation of hypersonic waves in polycrystalline silver films is due to scattering processes at lattice defects.     

Nonlinear optical characteristics of carbon disulfide

The nonlinear refractive index γ of CS₂ is studied using laser pulses of various durations (from 110 fs to 75 ns). It is found that γ increases with increasing pulse duration within the picosecond region (from (3 ± 0.6) × 10^?15 cm² W^?1 at 110 fs to (3.5 ± 0.7) × 10^?14 cm² W^?1 at 75 ns) due to orientational nonlinearities. Variations in the sign of γ caused by the thermal effect at different pulse durations and repetition rates are analyzed. It is demonstrated that the fast electronic component, the component associated with molecular processes, causing positive nonlinear refraction, and the acoustic component, responsible for negative nonlinear refraction, manifest themselves simultaneously. The results of a study of the nonlinear absorption of carbon disulfide are presented. The two-and three-photon absorption coefficients of CS₂ are determined to be (5 ± 1.5) × 10^?11 cm W^?1 and (2.8 ± 0.8) × 10^?23 cm³ W^?2, respectively.     

Investigation of third-order optical nonlinearity in KBe2BO3F2 crystal by Z-scan

The third-order optical nonlinearity of deep-ultraviolet (DUV) nonlinear optical (NLO) crystal KBe₂BO₃F₂ (KBBF) was investigated using single-beam Z-scan technique for the first time. The Z-scans were performed on a c-cut KBBF crystal and a KBBF prism-coupling device (PCD) with picosecond pulses at 355?nm. No two-photon absorption was observed in the experiment. The measured nonlinear refraction index n ₂ showed positive signs, indicating self-focusing Kerr effects. The n ₂ values were estimated to be (1.75±0.35)×10^?15?cm²/W with the c-cut sample and (1.85±0.37)×10^?15?cm²/W with the PCD, corresponding to the third-order nonlinear optical susceptibilities $\chi_{\mathrm{eff}}^{(3)}$ of (0.99±0.20)×10^?13?esu and (0.94±0.19)×10^?13?esu, respectively. The results are expected to promote the investigation of frequency conversion processes with ultra-short laser in KBBF crystal.     

Die Diffusionskoeffizienten und mittleren freien Weglängen der geladenen und neutralen Radon-Folgeprodukte in Luft

The knowledge of the diffusion coefficients of radioactive atoms and ions in air is very important in a number of investigations on and computations of the attachment of radon decay products to aerosol particles. In this work measurements of the diffusion coefficients of neutral and charged²¹²Pb atoms are reported. The values found areD ₀=(7.6±0.4)·10^?2cm²s^?1 for neutral atomsD=(5.0±0.3)·10^?2cm²s^?1 for charged atoms The used method of measurement allowed to determine these constants 1–5 seconds after the formation aged²¹²Pb atoms, so that a “cluster” formation was improbable. The mean free path for neutral (λ₀=(4.9±0.3)·10^?6cm) and charged (λ=(3.2±0.2)· 10^?6cm) lead 212 atoms in air were computed from the measured diffusion coefficients. All obtained results were compared with values, calculated from theory.     

Low temperature vibrational relaxation of OD in the A2Σ, state

The vibrational relaxation of the A ²Σ state of OD has been studied in the low translational temperature environment of an argon free-jet (T_trans near 5 K). Using laser induced fluorescence (LIF), the absolute vibrational relaxation rate coefficients were measured for OD A²Σ (ν′) to be 7.1 ± 2.6 × 10^?11, 5.9 ± 1.4 × 10^?11, and 2.7 ± 1.1 × 10^?11 cm³ s^?1 for the ν = 3, 2 and 1 states, respectively. State-to-state relaxation rate coefficients were also obtained for the ν= 1, ? = 1 level going to ν= 0, ? levels in the A²Σ manifold. The rotational relaxation rate coefficient for ν= 1, ?= 1 in the A state of OD was found to be 9.6 ± 1.0 × 10^?11cm³s^?1. These values are consistent with values measured for OH A²Σ, and the total loss rates are near the capture rate coefficient value. The vibrational relaxation rate coefficients k_ν appear to be governed by the vibrational energy of the molecule rather then by interaction with nearby dissociative states such as the a⁴Σ state. The relative Einstein A factors for the A²σ (ν = 3) state of OD were determined and compared with the available calculated value.     

Tunnelling splittings in the high resolution microwave and UV spectra of the benzonitrile—water complex: modelling the internal motion in its S0 and S1 states

Refined values of the barriers to internal motion in the 1:1 complex between benzonitrile and water in the gas phase have been determined from analyses of its fully resolved microwave and ultraviolet spectra. Both spectra exhibit tunnelling splittings associated with this motion. Modelling this behaviour using a semi-rigid Hamiltonian for an internal rotation of water around its C ₂ axis yields values of V ₂ = 440 ± 30 cm^?1 and 450 ± 30 cm^?1 in the ground and excited electronic states, respectively. These relatively high barriers are a consequence of two hydrogen bonds between the interacting species.