Pump power dependence in resonance femtosecond stimulated Raman spectroscopy

Femtosecond stimulated Raman spectroscopy (FSRS) has emerged as a powerful new technique that is capable of obtaining resonance Raman spectra of fluorescent species and transient photochemical intermediates. Unlike related transient infrared absorption techniques, the FSRS signal is quite sensitive to the laser power utilized in the vibrational probing event. In particular, FSRS spectra are highly sensitive to the intensity of the picosecond Raman‐pump pulse. We have measured the power dependence of the FSRS signal using pulse energies from ~10⁻⁹ to ~10⁻⁵ J and molecules with a range of molar absorptivities at the Raman‐pump wavelength of 400 nm, including β‐carotene (ε₄₀₀ = 58 300 M⁻¹ cm⁻¹), para‐nitroaniline (17 800 M⁻¹ cm⁻¹), nitronaphthalene (247 M⁻¹ cm⁻¹) and ferrocene (57 M⁻¹ cm⁻¹). We show that for strongly absorbing molecular systems, such as β‐carotene and para‐nitroaniline, the ground‐state (GS) FSRS signal actually decreases with increasing pump power at pump fluences above ~10⁻² J cm⁻², due to depletion of the GS population. However, for weakly absorbing species like nitronaphthalene and ferrocene, the signal increases linearly with increasing pump fluence until ~0.5 J cm⁻², at which point two‐photon absorption by the solute induces nonlinear absorption of the pump pulse and attenuation of the FSRS signal. The data are quantitatively simulated with a photophysical kinetic model, and the results are analyzed to provide simple guidelines for acceptable Raman‐pump powers in resonance FSRS experiments. The acceptable Raman‐pump power is proportional to the focused beam area and depends inversely on the sample's molar absorptivity. Copyright © 2013 John Wiley & Sons, Ltd.     

Molecular and atomic adsorption states of oxygen on Cu(111) at 100–300 K

Adsorption states of oxygen on Cu(111) at 100–300 K were investigated by means of HREELS. Two molecular species were characterized by different OO stretching frequencies (v(OO)) at 610 cm⁻¹ and 820–870 cm⁻¹, which are assigned to the peroxo-like species (O²⁻₂) adsorbed in a bridged form and the one in a bidentate form bound on an atop site, respectively. The bridged peroxo species is preferred at the low coverage and the atop peroxo species becomes dominant at the higher coverage. In addition to the peaks due to the molecular oxygen, a peak assigned to v(CuO) of atomic oxygen was observed at 370 cm⁻¹ at the high coverage. The frequency of this mode was higher than the frequency reported for Cu(111) exposed to oxygen above 300 K, indicating that the adsorption state of atomic oxygen formed at 100 K is different from that above 300 K. The v(OO) modes became faint after annealing to 170 K because of O₂ dissociation. The v(CuO) mode of the atomic oxygen formed at 100 K remained up to 230 K and disappeared after annealing to 300 K. No desorption of O₂ was detected on annealing to 300 K. It was also found that vibrational spectra for adsorbed NH₃ are influenced by the adsorption states of atomic oxygen on Cu(111).     

Investigations of the spatio-temporal build-up of atomic oxygen inside the micro-scaled atmospheric pressure plasma jet

The ascent of atomic oxygen densities created inside the micro-scaled atmospheric pressure plasma jet has been investigated spatially resolved under parameter variations such as applied power, gas mixture and gas velocity using two-photon absorption laser induced fluorescence spectroscopy. Along the discharge channel an increase of the atomic oxygen density within the plasma is observed. The density shows an exponentially asymptotic convergence into an equilibrium close to the effluent. In the post-discharge effluent an exponential spatial decrease can be found. Typical ascent distances of a few hundreds of μm decrease with the applied power and increase with gas velocity and oxygen admixture. The maximum atomic oxygen density increases with applied power and admixed molecular oxygen up to more than 10¹⁶ cm^-3. An increase of the maximum atomic oxygen density with increasing gas velocity has been found. Optical emission spectroscopy measurements indicate a strong increase of the nitrogen emission at low gas flow rates along the channel.     

Detection of atomic oxygen by laser-induced fluorescence spectroscopy at 130 nm

VUV radiation generated by stimulated Raman scattering from H₂ and tunable around 130 nm is applied to the detection of atomic oxygen produced in a flow-tube. Concentrations in the range to the detection of atomic oxygen produced in a flow-tube. Concentrations in the range of 10¹⁰ to 10¹¹ O-atoms per cm³ lead to fluorescence signals that can easily be detected on a nanosecond timescale. We deduce that oxygen impurities generated by plasma-wall interaction in present-day tokamak experiments should be measurable with spatial and temporal resolution applying this vuv source.     

A vibrational characterisation of the O/A1(111) system: a reassignment of HREELS data

In light of recent STM measurements of the O/A1(111) system, we reassign the dipole active modes observed at low coverage to resolve discrepancies between the interpretation of Strong, Firey, deWette and Erskine [Phys. Rev. B 26 (1982) 3483], invoking subsurface oxygen, and a variety of other studies which find no evidence for surface oxygen. The STM results, which show that very small island sizes are stabilized over an exposure range up to ∼ 200 L with a total coverage ≤ 0.2 ML, are incompatible with the assumption of long range periodicity required for lattice dynamical modeling. The consequence is that vibrational modes polarized parallel to the surface may become dipole active. Within an Al₃O cluster model appropriate to exposures ≤ 3 L where most oxygen atoms are isolated species in three-fold hollow sites, the strong feature at 584 cm⁻¹ (72 meV) is still attributed to top-layer oxygen motion perpecdicular to the surface (the symmetric Al₃O stretch) but the second intense feature at 480 cm⁻¹ (60 meV) is assigned to the umbrella mode involving predominantly Al motion parallel to the surface rather than the motion of two AlO layers moving perpendicular to the surface out of phase with each other. The lowest frequency mode near 224 cm⁻¹ (28 meV) derives from the frustrated translation of the cluster perpendicular to the surface. At higher exposures (> 10 L) where multiple oxygen islands begin to appear, totally symmetric combinations of the E-derived asymmetric Al₃O stretching motion polarised nominally parallel to the surface become dipole allowed and can be assigned to the loss at 850 cm⁻¹ (105 meV), which was previously attributed to subsurface oxygen.     

Sub-Doppler Heterodyne Frequency Measurements near 5 μm with a CO-Laser Sideband System: Improved Calibration Tables for Carbonyl Sulfide Transitions

We present a series of sub-Doppler frequency measurements of carbonyl sulfide (OCS) rovibrational transitions covering the spectral region around 2050 cm⁻¹(61 THz). The absolute experimental uncertainties are between 21 and 84 kHz (Δν/ν = 3–14 × 10⁻¹⁰). In our spectrometer, tunable microwave sidebands are added to CO-laser lines and are used to saturate OCS transitions at low absorber pressure. The CO laser, plus a fixed-frequency sideband, is stabilized to the center of the OCS Lamb-dip signal and the laser frequency is measured against combination frequencies of two saturation-stabilized CO₂lasers. The determined OCS transition frequencies are combined with other data in a least-squares fit. These measurements improve the accuracy of several carbonyl sulfide bands for calibration purposes by one to two orders of magnitude. New molecular constants and detailed calibration tables between 860 and 3100 cm⁻¹are given.     

A miniaturized prototype of resonant banana-shaped photoacoustic cell for gas sensing

A resonant photoacoustic cell intended for laser-spectroscopy gas sensing is represented. This cell is a miniature imitation of a macro-scale banana-shaped cell developed previously. The parameters, which specify the cavity shape, are chosen so as not only to provide optimal cell operation at a selected acoustic resonance but also to reduce substantially the cell sizes. A miniaturized prototype cell (the volume of acoustic cavity of ∼5 mm³) adapted to the narrow diffraction-limited beam of near-infrared laser is produced and examined experimentally. The noise-associated measurement error and laser-initiated signals are studied as functions of modulation frequency. The background signal and the useful response to light absorption by the gas are analyzed in measurements of absorption for ammonia in nitrogen flow with the help of a pigtailed DFB laser diode oscillated near a wavelength of 1.53 μm. The performance of prototype operation at the second longitudinal acoustic resonance (the resonance frequency of ∼32.9 kHz, Q-factor of ∼16.3) is estimated. The noise-limited minimal detectable absorption normalized to laser-beam power and detection bandwidth is ∼8.07 × 10⁻⁸ cm⁻¹ W Hz^−1/2. The amplitude of the background signal is equivalent to an absorption coefficient of ∼2.51 × 10⁻⁵ cm⁻¹. Advantages and drawbacks of the cell prototype are discussed. Despite low absorption-sensing performance, the produced miniaturized cell prototype shows a good capability of gas-leak detection.     

Temperature-dependent 29Si NMR resonance shifts in lightly- and heavily-doped Si:P

Careful NMR measurements on a very lightly-doped reference silicon sample provide a convenient highly precise and accurate secondary chemical shift reference standard for ²⁹Si MAS-NMR applicable over a wide temperature range. The linear temperature-dependence of the ²⁹Si chemical shift measured in this sample is used to refine an earlier presentation of the paramagnetic (high-frequency) ²⁹Si resonance shifts in heavily-doped n-type silicon samples near the metal–nonmetal transition. The data show systematic decreases of the local magnetic fields with increasing temperature in the range 100–470 K for all samples in the carrier concentration range from 2×10¹⁸ cm⁻³ to 8×10¹⁹ cm⁻³. This trend is qualitatively similar to that previously observed for the two-orders of magnitude larger ³¹P impurity NMR resonance shifts in the same temperature and concentration ranges. The ²⁹Si and ³¹P resonance shifts are not related by a simple scaling factor, however, indicating that impurity and host nuclei are affected by different subsets of partially-localized extrinsic electrons at all temperatures.     

The interaction of CO and O2 with the (111) surface of Pt3Ti

The electronic properties of clean and partly oxidized Pt₃Ti(111) surfaces have been studied utilizing carbon monoxide both as a probe and as a reducing agent. Vibrational frequencies and desorption profiles of chemisorbed CO as well as ion scattering and angular resolved X-ray photoelectron spectroscopy (XPS) suggest that the first atomic layer of annealed Pt₃Ti(111) is quasi-pure platinum. Scarcely any (θ ≈ 0.01) dissociation of CO was observed. Minor shifts of vibrational frequencies and desorption temperatures compared to Pt(111) and a p(2 × 2) “reconstruction” of the clean surface reveal some influence of the bulk. Auger spectroscopy, XPS, and ion scattering all show an increased titanium signal as a result of oxidation. Surface bound atomic oxygen gives a vibrational band around 650 cm⁻¹ which coincides with infrared absorption spectra of TiO₂. Flashing with CO shifts the band to 500 cm⁻¹. Correlated with this shift we observe (i) CO₂ desorption at a temperature well above that observed for Pt(111)/O, (ii) an altered Ti XPS signal, and (iii) a reduced oxygen concentration. Subsequently adsorbed CO molecules vibrate at the same frequencies as on the bare surface, give the same c(4 × 2) LEED pattern, and desorb at the same temperatures but with reduced intensity, in all proving that the surface oxide only acts as a site-blocker with respect to the metal surface. Our current understanding of these observations is that oxygen creates “islands of TiO₂”, segregated to the surface but with no electronic influence on remaining areas of the platinum enriched metal surface. The hexacoordinated Ti⁴⁺ ions on the surface of these islands are reduced by CO to pentacoordinated Ti³⁺ species. The vibrational shift, 650 to 500 cm⁻¹, can be understood by the dipole active bands of a triatomic O−Ti⁴⁺ −O vibrator compared to a diatomic Ti³⁺−O vibrator.     

ESR of silicon oxide thin-film capacitors

Amorphous thin films of silicon oxide deposited by the evaporation of silicon monoxide powder show an unresolved ESR signal with g values between 2.006 and 2.014. Spin densities of the order of 10¹⁹ cm⁻³ were measured, depending strongly on the preparation and annealing conditions. It is probable that unsaturated oxygen bonds are responsible for the ESR signal. It is believed that electric conduction in thin silicon oxide films is due to impurity ions and electronic conduction. In order to study the conduction mechanism in thin silicon oxide films, an electric field was applied simultaneously with the ESR measurements. Thin-film capacitors with the sandwich structure of CrAu/SiO/Au were used. The thickness of the silicon oxide films was between 4000 and 7000 Å. Electric fields of less than 10⁷ V/cm were applied.     

K-line X-ray fluorescence from highly charged iron ions under dense astrophysical plasma conditions

In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 10⁵ to 10⁷ K and an electron density ranging from 10¹⁸ to 10²² cm⁻³. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions.     

K-shell aluminum resonance line ratios for plasma diagnosis using spot spectroscopy

Using a detailed atomic model of K shell aluminum ions, we have calculated four diagnostic resonance line ratios as a function of temperature and density for cylindrical aluminum plasmas of diameter 50 and 100 μm, assumed in collisional-radiative equilibrium. The ion densities vary from 10¹⁹ cm^-3 to 10²¹ cm^-3, the temperatures range from 200 to 700 eV. The conditions are applicable to experiments using the spot spectroscopy technique for plasma diagnosis.     

Observations of 63 μm atomic oxygen emission in the earth's atmosphere from balloon altitudes: Astronomical implications

Measurements of ³P₁ → ³P₂ 63 μm atomic oxygen (OI) emission in the earth's atmosphere obtained with a balloon-borne telescope and high-resolution Fourier transform spectrometer are presented. Three results emerge from analysis of this data: (i) the frequency of the OI ³P₁ → ³P₂ transition was determined to be 158.2693 ± 0.003 cm⁻¹; (ii) the integrated line intensity of the atmospheric OI emission was determined to be 2.4 ± 0.5 · 10⁻⁵ W m⁻² sr⁻¹; and (iii) the integrated line intensity of the atmospheric OI emission was found to be constant over a range of zenith angles corresponding to air-mass values between 1.27 and > 20. The implications of these results on astronomical observations of OI emission are discussed.     

Overlapping spectral features and new assignment of 2‐propanol in the C–H stretching region

The vibrational spectra of gaseous and liquid 2‐propanol in the C–H stretching region of 2800 ~ 3100 cm⁻¹ were investigated by polarized photoacoustic Raman spectroscopy and conventional Raman spectroscopy, respectively. Using two deuterated samples, that is, CH₃CDOHCH₃ and CD₃CHOHCD₃, the overlapping spectral features between the CH and CH₃ groups were identified. With the aid of depolarization ratio measurements and density functional theory calculations, a new spectral assignment was presented. In the gas phase, the band at 2884 cm⁻¹ was assigned to the overlapping of one CH₃ Fermi resonance mode and a CH stretching of gauche conformer. The bands at 2917 and 2933 cm⁻¹ were assigned to another two CH₃ Fermi resonance modes, but the latter includes weak contribution from CH stretching of trans conformer. The bands at 2950 and 2983 cm⁻¹ were assigned to CH₃ symmetric and antisymmetric stretching, respectively. The spectral features of liquid 2‐propanol are similar to those in the gas phase except for the blue shift of CH and the red shift of CH₃ band positions, which can be attributed to the intermolecular interaction in the liquid state. The new assignments not only clarify the confusions in previous studies from different spectral methods but also provide the reliable groundwork on spectral application of 2‐propanol in the futures. Copyright © 2014 John Wiley & Sons, Ltd.     

Measurement of excited state number densities of oxygen and nitrogen in a non-equilibrium plasma

Number densities of several excited states of atomic oxygen and nitrogen have been measured in the decaying non-thermal plasma of a θ-pinch afterglow. The spatial variation of the electron density and temperature as functions of time after initiation of main bank discharge have also been measured to facilitate a comparison of the excited state number densities with model calculations. Measurements of the atomic oxygen excited states indicate that quintet to triplet spin exchange collisions and doubly excited states must be included in the model. The measured populations of the excited atomic nitrogen states agree well with those calculated at high density (N_e≈ 10¹⁴ cm^?3), but disagree badly at lower densities (N_e ≈ 10¹² cm^?3). The discrepancies seem to be real since they are larger than expected measurement uncertainty.     

硅、锗中氧的低温红外吸收

在6—300K下,利用红外傅里叶光谱仪研究了400—4000cm^-1间的硅、锗中氧的红外吸收。采用高分辨条件时,分辨率可达0.5cm^-1。研究了在低温下利用硅的1106cm^-1吸收峰和锗的855cm^-1吸收峰探测硅和锗氧含量的探测限和误差。若样品厚度为2cm,估计在20K下,硅中氧含量探测限～9.6×10¹⁴氧原子·cm^-3,锗中氧含量探测限～3.0×10¹⁴氧原子·cm^-3。同时,对不同生长条件下直拉锗单晶的氧含量进行了研究,并与用锂沉淀法所求得的锗中氧含量加以比较。对不同氧含量的硅样品的1106cm^-1吸收峰在6—300K的变化进行了观察和讨论。 关键词：     

Measurement of the absolute Raman scattering cross sections of sulfur and the standoff Raman detection of a 6‐mm‐thick sulfur specimen at 1500 m

The absolute Raman scattering cross sections (σ_RS) for the 471, 217, and 153 cm⁻¹ modes of sulfur were measured as 6.0 ± 1.2 × 10⁻²⁷, 7.7 ± 1.6 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁶ cm² at 815, 799, and 794 nm, respectively, using a 785‐nm pump laser. The corresponding values of σ_RS at 1120, 1089, and 1081 nm were determined to be 1.5 ± 0.3 × 10⁻²⁷, 1.2 ± 0.24 × 10⁻²⁷, and 1.2 ± 0.24 × 10⁻²⁷ cm² using a 1064‐nm laser. A temperature‐controlled, small‐cavity (2.125 mm diameter) blackbody source was used to calibrate the signal output of the Raman spectrometers for these measurements. Standoff Raman detection of a 6‐mm‐thick sulfur specimen located at 1500 m from the pump laser and the Raman spectrometer was made using a 1.4‐W, CW, 785‐nm pump laser. Copyright © 2010 John Wiley & Sons, Ltd.     

Search for muons from the direction of cygnus X-3

Muons and multimuons detected in the Fréjus underground nucleon decay detector between February 1984 and January 1986 have been analyzed. No excess events are observed in the direction of Cygnus X-3, which yields a 90% confidence level upper flux limit of 0.8 × 10⁻¹² cm⁻² s⁻¹, for an average rock overburden of 5000 hg cm⁻² corresponding to energies ⪆ 3 TeV. Using the 4.79 h periodicity of Cygnus X-3, no signal is found in any phase interval.     

Saturated two-photon absorption by calcium atoms in a perturber bath

This study was performed with calcium vapor at about 750°C perturbed by He at densities between 0.5 x 10¹⁹ and 5 x 10¹⁹ atoms/cm³ and under continuous laser intensities up to 10 kW/cm². The collisional absorption profile of the calcium intercombination line (657.5nm) has been obtained from fluorescence measurements and by using theoretical expressions. The saturation rates give the collisional decay rates of the atomic levels involved. The formation of exciplex species is suggested in order to interpret some of the experimental results.     

Raman scattering investigations on Co-doped ZnO epitaxial films: Local vibration modes and defect associated ferromagnetism

Raman scattering spectroscopy has been performed on high quality Co-doped ZnO epitaxial films, which were grown on Al₂O₃ (0001) by oxygen-plasma assisted molecular beam epitaxy. Raman measurements revealed two local vibration modes (LVMs) at 723 and 699 cm⁻¹ due to the substitution of Co²⁺ in wurtzite ZnO lattice. The LVM at 723 cm⁻¹ is found to be an elemental sensitive vibration mode for Co substitution. The LVM at 699 cm⁻¹ can be attributed to enrichment of Co²⁺ bound with oxygen vacancy, the cobalt–oxygen vacancy–cobalt complexes, in Zn_1−xCo_xO films associated with ferromagnetism. The intensity of LVM at 699 cm⁻¹, as well as saturated magnetization, enhanced after the vacuum annealing and depressed after oxygen annealing.