Elementary reactions of formyl (HCO) radical studied by laser photolysis—transient absorption spectroscopy

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV–Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH₃ → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8–100 bar and the temperature range 498–769 K. Reactions (2a), (2b), (2c), (3a) and (3b) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: k₁(He) = (0.8 ± 0.4) × 10⁻¹⁰exp(−(66.0 ± 3.4) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) × 10⁻¹⁸ cm² molecule⁻¹ at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2a), (2b), (2c), (3a) and (3b) are: k₂ = (3.6 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ (298 K); k₃ = (9.3 ± 2.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹(298 and 588 K).     

Intersubband absorption in highly photoexcited semiconductor quantum wells

Transient mid infrared (MIR) absorption spectroscopy is used to investigate transitions between higher electronic subbands in semiconductor quantum well (QW) structures after interband photoexcitation with intense picosecond pulses in the visible spectral range. Our investigation focuses on the e₂–e₃ intersubband transition in an asymmetric undoped GaAs/AlGaAs QW structure. At an injected nonequilibrium carrier density of 1×10¹³ cm⁻²/QW, an e₂–e₃ absorption band at 99 meV with a spectral width of 5 meV is found. For a higher density studied, 3×10¹³ cm⁻²/QW, the band is broadened and blueshifted by 30 meV. Intersubband absorption signals are distinguished from free-carrier absorption signals in the MIR by their characteristic time behavior.     

Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking

A new technique of cavity enhanced absorption spectroscopy is described. Molecular absorption spectra are obtained by recording the transmission maxima of the successive TEM_oo resonances of a high-finesse optical cavity when a Distributed Feedback Diode Laser is tuned across them. A noisy cavity output is usually observed in such a measurement since the resonances are spectrally narrower than the laser. We show that a folded (V-shaped) cavity can be used to obtain selective optical feedback from the intracavity field which builds up at resonance. This induces laser linewidth reduction and frequency locking. The linewidth narrowing eliminates the noisy cavity output, and allows measuring the maximum mode transmissions accurately. The frequency locking permits the laser to scan stepwise through the successive cavity modes. Frequency tuning is thus tightly optimized for cavity mode injection. Our setup for this technique of Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) includes a 50 cm folded cavity with finesse ∼20 000 (ringdown time ∼20 μs) and allows recording spectra of up to 200 cavity modes (2 cm⁻¹) using 100 ms laser scans. We obtain a noise equivalent absorption coefficient of ∼5×10⁻¹⁰ cm⁻¹ for 1 s averaging over scans, with a dynamic range of four orders of magnitude.     

Nonlinear Refractive Index of Er3+-Doped Fiber and Its Application to Nonlinear Fiber Coupler

A large change in the refractive index originating in the transition absorption of erbium ions is induced in an Er³⁺-doped fiber. It is shown that the Er³⁺-doped fiber exhibits the nonlinear refractive index of n₂=7.4 × 10⁻¹⁵ m²/W, which is 10⁵−10⁶ times larger than that caused by the optical Kerr effect in a usual silica fiber at the pumping, wavelength of 514.5 nm. The large nonlinear refractive index occurred in a fiber directional coupler fabricated with the Er³⁺-doped fiber optically changes the coupling condition. The coupling ratio changes up to 0.16 by increasing the pumping power up to 0.7 mW.     

Characteristics of InAlGaAs/InAlAs Superlattice Avalanche Photodiodes for Ultra-low Optical Power Detection in the Near Infrared

Static characteristics of two different structured InAlGaAs/InAlAs superlattice avalanche photodiodes (SLAPDs) cooled by liquid nitrogen were evaluated at a wavelength of 1.5 μm. The dark current of the SLAPD having a thick superlattice layer of 0.504 μm was 5 × 10⁻¹³ A. This was successively reduced by four orders of magnitude compared to that of the thin layer SLAPD of 0.231 μm at a breakdown voltage of around 20 V. The thickened layer was effective in suppressing tunneling dark current. An output current of 1.7×l0⁻¹² A at a bias voltage of 15 V was measured for an optical input with a wavelength of 1.5 μm and a signal power of 1 × 10⁻¹² W. This showed a sharp distinction from the dark current.     

Preparation and electrical properties of a pyrochlore-related Ce2Zr2O8−x phase

A pyrochlore-related Ce₂Zr₂O_8−x phase has been prepared in a reduction reoxidation process from Ce_0.5Zr_0.5O₂ powders. Ce₂Zr₂O_8−x, based on a cubic symmetry with a=1.053 nm, decomposes in nitrogen at 800 °C, but remains stable up to 900 °C in air. It shows mixed oxygen ionic and electronic conductivity. The bulk conductivity at 700 °C is 4×10⁻⁴ S cm⁻¹ in air and 1×10⁻² S cm⁻¹ in nitrogen, and the activation energy is 1.27 eV in air. In nitrogen, the Arrhenius law is not obeyed, and a curved plot was obtained from 400 to 700 °C; then, the conductivity decreased rapidly due to the thermal decomposition of Ce₂Zr₂O_8−x.     

Low resistance nonalloyed Al-based ohmic contacts on n-ZnO:Al

We have investigated the electrical properties of nonalloyed Al, Al/Au, and Al/Pt ohmic contacts on n-type ZnO:Al (2×10¹⁸ cm⁻³). All Al-based nonalloyed ohmic contacts on the n-ZnO:Al reveal linear current–voltage behavior with low specific contact resistivity of 8.5×10⁻⁴ (Al), 8.0×10⁻⁵ (Al/Au) and 1.2×10⁻⁵ Ω cm² (Al/Pt), respectively. Using secondary ion mass spectroscopy (SIMS) and x-ray photoelectron spectroscopy (XPS) depth profiles, it was found that the O atoms in the ZnO:Al layer outdiffused to Al metal layer while the Al atoms indiffused to the surface region of ZnO:Al. This interdiffusion between Al and O atoms at room temperature results in an increase of doping concentration in the surface region of the ZnO:Al and reduces a specific contact resistivity of the Al-based ohmic contacts without thermal annealing process.     

H2S : First Observation of the (70,0) Local Mode Pair and Updated Global Effective Vibrational Hamiltonian

The absorption spectrum of H₂S has been recorded by intracavity laser absorption spectroscopy in the spectral region 16 180–16 440 cm⁻¹ corresponding to an excitation of the (70^±, 0) local mode pair. Seventy-seven sublevels could be rotationally assigned and fitted with a rms of 0.009 cm⁻¹ by considering the (70^±, 0) local mode pair as isolated. The corresponding vibrational terms combined with all the levels reported in the literature were used to refine the effective vibrational Hamiltonian parameters of H₂³²S. The importance of the Fermi-type interaction is discussed.     

Structural properties of 10 μm thick InN grown on sapphire (0001)

The structural properties of a 10 μm thick In-face InN film, grown on Al₂O₃ (0001) by radio-frequency plasma-assisted molecular beam epitaxy, were investigated by transmission electron microscopy and high resolution x-ray diffraction. Electron microscopy revealed the presence of threading dislocations of edge, screw and mixed type, and the absence of planar defects. The dislocation density near the InN/sapphire interface was 1.55×10¹⁰ cm⁻², 4.82×10⁸ cm⁻² and 1.69×10⁹ cm⁻² for the edge, screw and mixed dislocation types, respectively. Towards the free surface of InN, the density of edge and mixed type dislocations decreased to 4.35×10⁹ cm⁻² and 1.20×10⁹ cm⁻², respectively, while the density of screw dislocations remained constant. Using x-ray diffraction, dislocations with screw component were found to be 1.2×10⁹ cm⁻², in good agreement with the electron microscopy results. Comparing electron microscopy results with x-ray diffraction ones, it is suggested that pure edge dislocations are neither completely randomly distributed nor completely piled up in grain boundaries within the InN film.     

Hard X-ray generation from microdroplets in intense laser fields

Microdroplets of 15-μm diameter are subjected to ultra-short laser pulses of intensities up to 10¹⁵Wcm⁻² to produce hot dense plasma. The hot electrons produced in the microdroplet plasma result in efficient generation of hard X-rays in the range 50–150keV at an irradiance as low as 8×10¹⁴Wcm⁻². The X-ray source efficiency is estimated to be about 2 ×10⁻⁷%. A prepulse that is about 11ns ahead of the main pulse strongly influences the droplet plasma and the resulting X-ray emission. For a similar laser prepulse and intensity, no measurable hard X-ray emission is observed when the laser is focused on a solid target of similar composition and this indicates that liquid droplet targets are best suited for hard X-ray generation in laser–plasma interactions.     

Study of the interaction of Na9[SbW9O33]·19.5H2O with bovine serum albumin: Spectroscopic and voltammetric methods

The interaction of Na₉[SbW₉O₃₃]·19.5H₂O (SbW) with bovine serum albumin (BSA) is studied by spectroscopic and voltammetric methods. Absorption spectroscopy of BSA and the linear sweep voltammetry of SbW proved the formation of ground-state SbW–BSA complex. Fluorescence quenching of serum albumin by SbW is also found to be a static quenching process. The binding constant K_a is 4.13×10⁴ L mol⁻¹ for SbW–BSA at pH 7.40 Tris–HCl buffer at 295 K. The number of binding sites and the apparent binding constants at different temperatures are obtained from the analysis of the fluorescence quenching data. The thermodynamic parameters determined by the Van’t Hoff analysis of the binding constants (ΔH=−80.01 kJ mol⁻¹ and ΔS=−182.85 J mol⁻¹ K⁻¹) clearly show that the binding is absolutely entropy driven. Hydrogen bonding and van der Waals interaction force play major role in stabilizing the complex. The effect of SbW on the conformation of BSA is analyzed using synchronous fluorescence spectroscopy.     

Vacuum quantum effect for curved boundaries in static Robertson–Walker space–time

The energy–momentum tensor for a massless conformally coupled scalar field in the region between two curved boundaries in k=−1 static Robertson–Walker space–time is investigated. We assume that the scalar field satisfies the Dirichlet boundary condition on the boundaries. k=−1 Robertson–Walker space is conformally related to the Rindler space, as a result we can obtain vacuum expectation values of energy–momentum tensor for conformally invariant field in Robertson–Walker space from the corresponding Rindler counterpart by the conformal transformation.     

Effective indexes of refraction and limiting properties of ethyl red

With the Z-scan method, the nonlinear optical properties of ethyl red (ER) in ethanol solution are measured by using the lasers of 441.6, 535 and 633 nm, respectively. As a result, the effective indexes of refraction n₂ of CR at the three wavelengths are in the range from 10⁻¹⁰ to 10⁻⁹ m² W⁻¹. The nonlinear absorption of ER ethanol film at the three wavelengths is measured respectively. The self-diffraction of the ER solution at 441.6 and at 535 nm is investigated, respectively, and the results indicate it possesses high quality of optical limiting.     

Resonant photoacoustic detection of trace gas with DFB diode laser

A resonant photoacoustic detection system based on a low-power distributed feedback diode laser is developed. This sensor has been applied to the detection of acetylene (C₂H₂) using a specifically designed photoacoustic cell operating on its second longitudinal mode. The minimum detectable limit of about 10 parts-per-million volume (SNR=1) is achieved with an average laser power of 3.5 mW at atmospheric pressure, and an integration time constant of 3 ms; thus, the minimum detectable absorption coefficient normalised by power and bandwidth is 4.0×10⁻⁸ W cm⁻¹/√Hz. The optimum operating pressure buffered with N₂ is also investigated. The realisation of our system is described and experimental results are compared with different modulation techniques and other results reported in the literature. A number of issues arising from the conventional use of mechanical chopping of the beam can be effectively suppressed in wavelength modulation PA spectroscopy (WM-PAS) and second harmonic detection.     

Study on nonlinear optical absorption properties of [(CH3)4N]2[Cu(dmit)2] by Z-scan technique

The third-order optical nonlinearities of an organo-metallic compound, [(CH₃)₄N]₂[Cu(dmit)₂] (dmit²⁻=4,5-dithiolate-1,3-dithiole-2-thione), abbreviated as MeCu, dissolved in acetone are characterized by Z-scan technique with picosecond and nanosecond laser pulses in the near-infrared region. Two-photon absorption has been found when the sample solution is irradiated by 40 ps pulse width at 1064 nm and the two-photon absorption (TPA) coefficient β_TPA is 4×10⁻¹³ m/W. While excited by 15 ns laser pulses at 1053 nm, the Z-scan spectra reveal strong reverse saturable absorption (RSA) and the nonlinear absorption coefficient β_RSA is estimated to be as high as 7.07×10⁻¹¹ m/W which is much larger than β_TPA. An explanation for this enhancement is given. All the results suggest that MeCu may be a promising candidate for the application to optical limiting in the near-infrared region.     

ICLAS of HDO between 13,020 and 14,115 cm

The high resolution absorption spectrum of monodeuterated water, HDO, has been recorded by Intracavity Laser Absorption Spectroscopy (ICLAS) in the 13,020–14,115 cm⁻¹ region dominated by the 4ν₃ band. The achieved noise equivalent absorption (α_min10⁻⁹ cm⁻¹) allowed detecting transitions with line strengths as small as 2×10⁻²⁷ cm/molecule which is about 10 times lower than the smallest line intensities previously detected in the region.The rovibrational assignment of the spectrum was based on the results of the variational calculations of Schwenke and Partridge (SP) as well as recent calculations using a new potential energy surface performed by Voronin, Tolchenov and Tennyson (VTT). 2157 transitions involving 21 upper vibrational states were assigned to HD¹⁶O while only four bands were previously reported in the region. A set of 157 new energy levels could be derived. It includes rotational levels of several highly excited bending states, in particular the (0 11 0) pure bending state. For some states like the (1 0 3) and (0 2 3) Fermi dyad, effective Hamiltonian modelling was needed to establish the vibrational assignments of some rotational levels. VTT calculations were found to significantly improve the SP results, the rms deviation of the calculated and observed energies being decreased from 0.23 to 0.06 cm⁻¹.Finally, 79 transitions of the 4ν₃ band of the HD¹⁸O isotopologue were assigned, leading to the derivation of 48 levels, which are the most excited energy levels reported so far for this isotopologue.     

High sensitivity CW-cavity ring down spectroscopy of CO2 near 1.35 μm (I): line positions

The absorption spectrum of carbon dioxide in natural isotopic abundance has been investigated by CW-cavity ring down spectroscopy with a new setup based on fibred distributed feedback (DFB) laser diodes. By using a series of 25 DFB lasers, the CO₂ spectrum was recorded in the 7123–7793 cm⁻¹ region with a typical sensitivity of 3×10⁻¹⁰ cm⁻¹. A 2125 transitions with intensities as low as 1×10⁻²⁹ cm/molecule were detected and assigned to the ¹²C¹⁶O₂, ¹⁶O¹²C¹⁷O and ¹⁶O¹²C¹⁸O isotopologues. For comparison, only 357 of them were previously reported from Venus spectra and 344 transitions were included in the 2004 version of the HITRAN database. The band by band analysis has led to the determination of the rovibrational parameters of 28, 2 and 6 bands for the ¹²C¹⁶O₂, ¹⁶O¹²C¹⁷O and ¹⁶O¹²C¹⁸O isotopologue, respectively. While the uncertainty on the experimental line positions is on the order of 5×10⁻⁴ cm⁻¹, the average deviation from the ¹²C¹⁶O₂ calculated values provided by the most recent version of the carbon dioxide spectroscopic databank (CDSD) is −2.8×10⁻³ cm⁻¹ with an root mean square (rms) deviation of 3.5×10⁻³ cm⁻¹. Maximum deviations in the order of 0.02 and 0.12 cm⁻¹ were evidenced for some bands of the ¹⁶O¹²C¹⁷O and ¹⁶O¹²C¹⁸O minor isotopologues. The obtained results improve significantly the previous measurements from Venus spectra and will be valuable to refine the sets of effective Hamiltonian parameters used to generate the CDSD database.     

Nonlinear optical properties of Cu nanocluster composite fabricated by 180 keV ion implantation

Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 5×10¹⁶ ions/cm² has been studied. The microstructural properties of the nanoclusters has been verified by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. Results of the investigation of nonlinear refraction by the off-axis Z-scan configuration were presented and the mechanisms responsible for the nonlinear response were discussed. Third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 8.7×10⁻⁸ esu at 532 nm and 6.0×10⁻⁸ esu at 1064 nm, respectively.     

The control of very low oxygen partial pressures with stabilized zirconia cell

Control of very low oxygen partial pressures was performed in the range of 10⁻²¹-10⁻²⁴ Pa at 750°C by pumping oxygen into the purified hydrogen stream with a stabilized zirconia cell. The oxygen partial pressures were monitored by a stabilized zirconia sensor. The stabilized zirconia oxygen sensor was calibrated by H₂-CO₂ gas buffer mixture in the range of oxygen pressure from 10⁻¹⁷ to 10⁻²¹ Pa, and oxygen partial pressures below 10⁻²¹ Pa were measured by extrapolating the calibration line to very low oxygen partial pressures. The lowest oxygen partial pressure controlled was 10⁻²⁴ Pa at 750°C, which was limited by gas leaks in the system and also by the reduction of the ionic transference number in solid electrolyte used as the oxygen pump.     

Effect of oxygen partial pressure on the structural and optical properties of dc reactive magnetron sputtered molybdenum oxide films

Molybdenum oxide films (MoO₃) were deposited on glass and crystalline silicon substrates by sputtering of molybdenum target under various oxygen partial pressures in the range 8 × 10⁻⁵–8 × 10⁻⁴ mbar and at a fixed substrate temperature of 473 K employing dc magnetron sputtering technique. The influence of oxygen partial pressure on the composition stoichiometry, chemical binding configuration, crystallographic structure and electrical and optical properties was systematically studied. X-ray photoelectron spectra of the films formed at 8 × 10⁻⁵ mbar showed the presence of Mo⁶⁺ and Mo⁵⁺ oxidation states of MoO₃ and MoO_3−x. The films deposited at oxygen partial pressure of 2 × 10⁻⁴ mbar showed Mo⁶⁺ oxidation state indicating the films were nearly stoichiometric. It was also confirmed by the Fourier transform infrared spectroscopic studies. X-ray diffraction studies revealed that the films formed at oxygen partial pressure of 2 × 10⁻⁴ mbar showed the presence of (0 k 0) reflections indicated the layered structure of α-phase MoO₃. The electrical conductivity of the films decreased from 3.6 × 10⁻⁵ to 1.6 × 10⁻⁶ Ω⁻¹ cm⁻¹, the optical band gap of the films increased from 2.93 to 3.26 eV and the refractive index increased from 2.02 to 2.13 with the increase of oxygen partial pressure from 8 × 10⁻⁵ to 8 × 10⁻⁴ mbar, respectively.