Low-temperature absorption contour of the ν3 band of SF6

A band contour analysis is carried out for the ν₃ absorption in SF₆. Values of ΔB = ? (1.0 ? 1.5) × 10^?4cm^?1, ζ₃ = 0.701, and ν₀ = 948.2cm^?1 are found. Tentative assignments are given for the SF₆ rotational states which are pumped by the P(14) through P(22) lines of the CO₂ laser.     

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.     

Absorption of CO2 laser pulses at different wavelengths by ground-state and vibrationally heated SF6

The absorption of CO₂ laser pulses by low pressure SF₆ gas has been investigated over a wide range of energy fluxes. For laser energy fluxes of 0.01–1 J cm^-2 the effective absorption cross section varies between 0.2 and 2 × 10^-18 cm². For each laser line an individual dependence on the energy is found and in some cases minor changes in the absorption behaviour seem to occur around 0.1 J cm^-2. SF₆ excited with an average vibrational energy content of up to 20 photons/molecule does not absorb measurable amounts of 9.4 μm laser light. The influence of various SF₆ and Ar pressures on the temporal shape of the transmitted pulses has been investigated.     

Sulfur isotope enrichment in SF6 by high intensity CO2 laser radiation

Enrichment of ³⁴SF₆ following irradiation of SF₆?H₂ mixtures by the focused output of a pulsed TEA CO₂ laser has been studied as a function of the number of laser pulses, excitation wavelength, total pressure, and laser energy.     

Some aspects of CO2 laser induced fluorescence in SF6−H2 mixtures

Measurements in SF₆?H₂ mixtures of HF¹ fluorescence at 2.8 μm induced by pulsed CO₂ laser radiation are reported. The dependence of fluorescence intensity on laser fluence is found to be strongly affected by the laser beam geometry in the interaction region. Our results show that the technique of HF¹ fluorescence intensity detection can be a sensitive and reliable single-shot measure of multiple-photon dissociation of SF₆ in a collisionless regime on condition that the laser fluence is uniform along the interaction region which is monitored.     

Absorption spectra of C6H6 and C6D6 near 340 nm

The absorption spectra of C₆H₆ and C₆D₆ in the liquid phase have been studied near 340 nm. The absorption spectrophotometric mounting was a sequential double-beam attachment with linear response to energy on scanning of the spectrum before the exit slit and an electronic device which gives directly either the absorbance or the integrated absorbance of a transition and, consequently, its oscillator strength.The oscillator strength measured for the band of C₆H₆ is 8×10^?8, which corresponds to a dipole moment of 2.4×10^?3 Debye; this value is of the same order as a theoretical value calculated by Tsubomura and Mulliken (3.8×10^?3 Debye) for a transition between states ³F and ³A of an oxygen-benzene pair. This agreement corroborates the hypothetical existence of such a transition.The first vibrational band is at 28553 cm^?1 for C₆H₆; this band is not observed in the vapor or solid phase. It corresponds probably to the transition 0-0, which is considered in the literature to be near 29500 cm^?1. The isotopic shift measured for this first band is 164 cm^?1. The vibrational frequencies are, respectively, 910 cm^?1 for C₆H₆ and 889 cm^?1 for C₆D₆.     

The forbidden far-infrared ν6 band of SF6

The far infrared spectra of SF₆ in the 33-μm region in the gas phase at different pressures and in the liquid phase have been studied. A small band situated at 351 cm^?1 on the high-frequency side of two difference bands situated at 304.5 cm^?1 has been observed in the gas phase. Since the integrated intensity of the 351-cm^?1 band varies linearly with the density, it cannot be collision induced. It appears that it is the forbidden ν₆ band that becomes active by Coriolis interaction. This band is seen in the liquid at about the same frequency when it is deconvoluted from the neighboring broadened and split difference bands.     

Laser Stark spectroscopy of thioformaldehyde in the 10-μm region: The ν3, ν4, and the ν6 fundamentals

The ν₃, ν₄, and ν₆ bands of thioformaldehyde, H₂CS, have been studied using the technique of laser Stark spectroscopy. The H₂CS was produced by the pyrolysis of dimethyl disulfide, and the spectrum was observed using a multipass absorption cell. The band origins are ν₃, 1059.2037 cm^?1; ν₄, 990.1866 cm^?1; and ν₆, 991.0149 cm^?1. The band previously assigned as 2ν₆ has been reassigned as 2ν₂, leading to a value of the ν₂ band origin of ca. 1439 cm^?1. Rotational constants and dipole moments of the vibrational states have been determined.     

Diode laser spectrum of the ν3 band of 34SF6

A diode laser was used to measure the absorption spectrum of the ν₃ band of ³⁴SF₆. This isotopic species, which is present in the natural sample (4.2%), was cooled in a molecular beam of pure SF₆. Subbranches up to J = 22 were recorded and identified. The molecular parameters, determined with a simple fitting procedure, are compared with those known of ³²SF₆ and ³³SF₆.     

SF6 ground-based infrared solar absorption measurements: long-term trend, pollution events, and a search for SF5CF3 absorption

Infrared solar spectra recorded with the Fourier transform spectrometer in the McMath solar telescope complex on Kitt Peak (31.9°N latitude, 111.6°W, altitude), southwest of Tucson, Arizona, have been analyzed to retrieve average SF₆ tropospheric mixing ratios over a two-decade time span. The analysis is based primarily on spectral fits to absorption by the intense, unresolved ν₃ band Q branch at . A best fit to measurements recorded with SF₆ near typical background concentrations yields a SF₆ increase in the average tropospheric mixing ratio from (10⁻¹² per unit volume) in March 1982 to in March 2002. The long-term increase by a factor of 3.34 over the time span is consistent with the rapid growth of surface mixing ratios measured in situ at Northern Hemisphere remote stations, though the infrared measurements show a large scatter. Average tropospheric mixing ratio enhancements above background by 2-3 orders of magnitude have been identified in spectra recorded on 5 days between November 1988 and April 1997. These spectra were individually analyzed in an attempt to detect the strongest 8- band of SF₅CF₃, a molecule recently identified with an atmospheric growth that has closely paralleled the rise in SF₆ during the past three decades. Absorption by the strongest SF₅CF₃ band was predicted to be above the noise level in the Kitt Peak spectrum with the highest average mean tropospheric SF₆ mixing ratio, assuming the reported atmospheric SF₅CF₃/SF₆ ratio and a room temperature absorption cross sections reported for the SF₅CF₃ 903-cm⁻¹ band. An upper limit of 8×10¹⁵ for the SF₅CF₃ total column was estimated for this case. We hypothesize that the highly elevated SF₆ levels above Kitt Peak resulted from a local release experiment rather than production via electrochemical fluoridation of intermediate products, the proposed source of atmospheric SF₅CF₃. The absence of the SF₅CF₃ feature in the spectra with elevated SF₆ is consistent with the absence of SF₅CF₃ reported in a pure SF₆ sample.     

Infrared Spectroscopy of the ν1 Band of Sulfur Tetrafluoride, SF4

Infrared absorption spectra of the ν₁ axial S-F stretching vibrational bands of sulfur tetrafluoride, SF₄, have been recorded and analyzed. A diode-laser jet spectrometer was used to record high-resolution spectra of ³²SF₄, with 87 vibration-rotation lines of the ν₁ fundamental being assigned. Least-squares fitting of the data yielded a precise vibrational band origin, as well as rotational parameters for the upper state. In addition, lower-resolution spectra of a static sample of SF₄ held at room temperature were recorded using a Fourier transform (FTIR) spectrometer. The progressions of prominent features observed in the room-temperature FTIR spectra are attributed to summation bands arising from ν₁ transitions from excited vibrational levels of the low-frequency ν₄ manifold of both ³²SF₄ and ³⁴SF₄.     

Infrared diode laser spectroscopy of FCO: The ν1 and ν2 bands

The ν₁ (CO stretching) and ν₂ (CF stretching) bands of the FCO radical were observed with Doppler-limited resolution by an infrared diode laser spectrometer with Zeeman and source modulation. The FCO radical was generated by a 60-Hz discharge in one of the following three gas mixtures: O₂ + C₂F₄, CO + SF₆, and CO + C₂F₄, all diluted with He. The observed spectra were analyzed to determine the rotational constants, the centrifugal distortion constants, and the spin-rotation interaction constants. The band origins, 1861.6372(1) and 1026.1283(1) cm^?1 [with standard errors in parentheses], which were obtained, were found to agree well with matrix data, 1857 and 1023 cm^?1, respectively. The assignment of the observed spectra to the FCO radical was further supported by observing the ν₁ band of F¹³CO, which was obtained from ¹³CO and SF₆. The molecular structure and the force field of FCO are briefly discussed by using molecular constants obtained from the observed spectra.     

Collisionless dissociation and isotopic enrichment of SF6 using high-powered CO2 laser radiation

Dissociation of ³²SF₆ and the resultant isotopic enrichment of ³⁴SF₆ using high-powered CO₂ laser radiation has been studied with higher experimental sensitivity than previously reported. Enrichment factors have been measured as a function of laser pulse number, wavelength, energy and time duration. A geometry-independent dissociation cross section is introduced and measured values are presented. Threshold energy densities, below which no dissociation was observed, were also determined.     

High precision spectroscopy of SF6 with cw high pressure tunable CO2 laser

Investigations are reported on the frequency characteristics of the cw high pressure CO₂ laser and its use for high precision spectroscopy. The problem of using a cw tunable CO₂ laser with a mixture of a few isotopes (¹²C¹⁶O₂, ¹²C¹⁸O₂, ¹²C¹⁶O¹⁸O and others) in a cw high pressure tunable CO₂ laser is discussed. Broadening of the tuning range has given us the opportunity to find seven new absorption lines of SF₆ near the transition P(20) of the 00⁰1–10⁰0 band of the CO₂ laser.     

Muonic X-ray intensities in SF6 and in H2+SF6

With a high pressure gas target muonic F and S X-ray intensities in SF₆ and H₂+SF₆ have been measured. It was found that the distribution of muons between sulphur and fluorine is not at all equal to the ratio of the atomic numbers Z.     

High-resolution Raman spectroscopy of the ν1 region and Raman-Raman double resonance spectroscopy of the 2ν1−ν1 band of SF6 and SF6. Determination of the equilibrium bond length of sulfur hexafluoride

The ν₁ region of ³²SF₆ and ³⁴SF₆ has been studied by stimulated Raman spectroscopy. For both isotopomers, a detailed analysis has been performed. Several hot bands (ν₁+ν₆−ν₆, ν₁+2ν₆−2ν₆, ν₁+ν₅−ν₅) have been taken into account to calculate synthetic spectra that satisfactorily reproduce the experimental data. These results, together with the previous studies of the other fundamental bands have allowed us to determine the equilibrium bond length of sulfur hexafluoride as r_e=1.5560(1) Å, in very good agreement with recent ab initio calculations. The 2ν₁−ν₁ band has also been studied for both isotopomers by Raman-Raman double resonance spectroscopy and the resulting spectra have been analyzed. In this case, a striking difference is observed between the two isotopomers, since the 2ν₁−ν₁ band of ³⁴SF₆ appears to have a very narrow structure that could not be rotationally resolved under the present experimental conditions. All analyses have been performed thanks to the HTDS program suite (http://www.u-bourgogne.fr/LPUB/hTDS.html) dedicated to octahedral XY₆ molecules.     

Luminescence of Pr-doped LiCaAlF6 and LiSrAlF6 crystals

The spectral and kinetic parameters of LiCaAlF₆:Pr and LiSrAlF₆:Pr single crystals are studied at LHeT and room temperature (RT). Photon cascade emission (PCE), i.e., ¹S₀→¹I₆ and ³P₀→³H_j, ³F_j transitions after Pr³⁺ excitation via 4f²→4f 5d absorption results in the conversion of the vacuum ultraviolet photon to two visible photons. The excitation and photoemission spectra as well as decay times have been measured and compared with those for CaF₂:Pr and SrF₂:Pr crystals. X-ray luminescence was measured to study the emission origin from both ¹S₀ and ³P₀ states of Pr³⁺. An intense phosphorescence of LiSrAlF₆:Pr was observed in the visible range after X-irradiation at RT, contrary to LiCaAlF₆:Pr.     

Mo study on charge distributions in octahedral PF−6, AsF−6 and SbF−6 anions

The charge distributions in octahedral PF^?₆, AsF^?₆, and SbF^?₆ anions are studied by means of the ab initio molecular orbital method. We find that the central P, As, and Sb atoms are all positively charged in these anions, while F atoms negatively charged, the order of the positive charge being Sb > P > As.     

Influence of collisions and pulse intensity on multiple photon absorption in SF6

Using a pyroelectric detector, the multiple photon absorption (MPA) of the SF₆ molecule in a wide range of pressures (10^-3 -1 torr) has been studied. The significant role of collisions in MPA has been shown. The fraction of molecules excited under essentially collisionless conditions has been defined. It is shown that under collisionless excitation of SF₆ (p < 10^-2 torr) at energy fluences E < 10^-1 J/cm² the intensity of the laser pulse plays the essential role, while in presence of collisions MPA is determined mainly by the energy fluence in the pulse.     

High resolution infrared spectrum of the ν1 band of 14N16O2

The infrared spectrum of the ν₁ band of ¹⁴N¹⁶O₂ has been recorded with a resolution of about 0.025 cm^?1 in the region extending from 1480 to 1270 cm^?1. From about 1350 cm^?1, the absorption became progressively weaker and no absorption at all could be detected below the band origin located at 1319.797 cm^?1. Because series with low values of K_a could not be measured, constants which depend strongly upon the molecular asymmetry could not be determined.