Effect of broadband amplified spontaneous emission on absorption measurements in phase-shift off-axis cavity enhanced absorption spectroscopy

Phase-shift cavity enhanced absorption spectroscopy has been described for the case of an off-axis alignment of an optical cavity formed by high reflectivity mirrors. The effect of laser broadband amplified spontaneous emission (ASE) from a DFB diode laser (1605 nm) has been analysed for absorption measurements extracted from the phase-shift of the intensity modulated beam. A simple model has been proposed for extraction of actual absorption spectra and linestrengths from the phase and amplitude measurements. It has been shown that omitting the ASE contribution to the cavity output light intensity may lead to an overestimation of absorption linestrength.     

Absolute absorption measurements of polymer films for optical waveguide applications by photothermal deflection spectroscopy

A self‐contained experimental technique is proposed for measuring the absolute optical absorption spectra, thermal diffusivity, and thermal conductivity of polymer thin films. The technique is based on photothermal deflection spectroscopy and provides sensitivity that is high enough to quantify the very small optical absorption losses in polymer films used for optical waveguide applications. The capabilities of the technique are demonstrated with measurements performed on thin films of poly(methyl methacrylate) and a fluorinated polymer (CYTOP). An error analysis is presented, and the factors are discussed that influence the accuracy of the technique. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2717–2726, 2001     

Derivation of new equations for phase-shift cavity ring-down spectroscopy

Current phase-shift cavity ring-down spectroscopy (PS-CRDS) experiments make use of equations originally developed for fluorescence studies. As these equations fail to take the length of the optical cavity and the superposition of reflecting beams into account, they lose validity as the length of the cavity increases. A new set of equations, based solely on the principles of PS-CRDS, is developed for determining the ring-down time from either the phase shift or the intensity of the waveform exiting the cavity. It is shown that the PS-CRDS equations reduce to those developed for fluorescence study for short cavities. The new equations provide a more accurate method in determining the characteristic ring-down time and phase shift for long cavities, especially fiber optic cavities, which is promising in on-site chemical sensing.     

A thermal diffusion model of photothermal spectroscopy

A phenomenological theory of photothermal spectroscopy (PTS) is developed in which the temporal behavior of the PTS signal can be described and the relationship between the ordinary absorption spectra and PTS spectra is determined.     

Combustion measurement of thermoacoustic oscillating flames by diode-laser absorption spectroscopy sensors

Diode-laser absorption spectroscopy has been applied to a swirl-stabilized turbulent combustor to detect high frequency combustion oscillation and combustion state related to combustion noise. Two diode-laser absorption spectroscopy techniques of scanned-wavelength method and fixed-wavelength method are adopted. In the scanned-wavelength method, fluctuations of temperature and H₂O mole fraction up to 1 kHz are detected. Two dominant peak frequencies of power spectra of these fluctuations, which are about 125 Hz and 140 Hz, coincide with those of pressure fluctuation in the combustor. In the case of control by secondary fuel injection, the energy at peak frequency of temperature and H₂O mole fraction decreases in accordance with noise reduction. Similar to the combustion noise, temperature fluctuation shows a minimal value at the appropriate frequency of secondary fuel injection. By analysing transmitted signals, the fixed-wavelength method provides power spectra similar to those obtained by the scanned-wavelength method. The advantage of the fixed-wavelength method is capability of detection of high frequency combustion oscillation more than 1 kHz. These results prove that the diode-laser absorption spectroscopy has great applicability as sensors for the combustion measurement of thermoacoustic oscillating flames and active control of turbulent combustion.     

The measurement of stable isotope distribution using Zeeman atomic absorption spectroscopy

The possibilities of stable isotope analysis using AAS are pointed out. The different isotopic effects occurring in optical spectra are discussed and the influence of the isotopic distribution in a sample on the line profile including broadening effects is analysed.An apparatus, based on the Zeeman scanning technique, is described, which can detect variations in the natural isotopic distribution. Measurements were carried out using the intercombination lines of Hg, Cd and Zn.     

A comparison between electrokinetic capillary chromatography and absorption spectroscopy for the analysis of peptide-micelle association by weak hydrophobic interactions

Micellar electrokinetic capillary chromatography (MEKC) was compared to absorption spectroscopy to estimate equilibrium association constans (K(as)) for peptide-micelle systems involving three peptides (leucine-enkephalin, methionine-enkephalin and leucine-phenylalanine (LF)) and two surfactant micelles (sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB)). Buffer pH was chosen to minimize purely electrostatic interactions between peptides and micelles that could not be interrogated by absorption spectroscopy. Viscosity-corrected MEKC mobilities gave reasonably similar estimates of K(as) between the two methods for all three peptide-SDS micelle systems, with K(as) values ranging from 13.7 +/- 0.3 to 49 +/- 1 M(-1). For CTAB, estimates of K(as) for LF-CTAB micelle association were of the same order of magnitude as the SDS micelle by the two methods of estimation. On the other hand, enkephalin-CTAB micelle binding was about 10 times stronger (K(as) = 122 +/- 3 M(-1) to 311 +/- 9 M(-1)) than the enkephalin-SDS micelle binding. In addition, MEKC underestimated the K(as) values relative to spectroscopy by a factor of 2-3 for the enkephalin-CTAB system.     

Probing weak molecular orbital interactions in non-conjugated diene molecules by means of near-edge X-ray absorption spectroscopy

Carbon and oxygen near-edge X-ray absorption fine structure (NEXAFS) spectra of 1,4-cyclohexadiene, p-benzoquinone, norbornadiene, norbornadienone, and cis-cis-[4,4,2]propella-3,8-diene-11,12-dione were calculated by means of Hartree-Fock and hybrid density functional theory using the static-exchange (STEX) approximation. The NEXAFS spectra are used as a probe to identify weak molecular interactions between the two non-conjugated ethylenic pi* orbitals present in these molecules. We show that the X-ray absorption spectrum of 1,4-cyclohexadiene exhibits some particular spectral structures in the discrete energy region that evidence diene through-bond orbital interaction, whereas absorption peaks are identified in the norbornadiene and norbornadienone spectra that indicate effective through-space orbital interactions. The molecular structure of the cis-cis-[4,4,2]propella-3,8-diene-11,12-dione isomer is such that the indirect through-bond or through-space diene orbital interactions are too weak to be assigned by its C1s NEXAFS spectrum.     

Concentration modulated absorption spectroscopy

A new Concentration Modulation technique has been developed at the University College of Wales, Aberystwyth, U.K., capable of markedly extending the sensitivity limits in Absorption Spectroscopy. By relating Gain and Transmittance values direct measurement of spectroscopic concentrations become possible for the first time. The use of picosecond lasers enables lifetime determinations down to ∼ 20 ps. Some of the applications for this highly sensitive technique will be presented.     

Thermal relaxation of glycerol and propylene glycol studied by photothermal spectroscopy

In this paper we report on experimental data for the frequency and temperature dependence of the thermal properties of supercooled glycerol and propylene glycol. By using a photopyroelectric method the specific heat capacity and thermal conductivity were separately determined in a bandwidth of several decades. We have recently shown that the thermal conductivity has no relaxation behavior, which simplifies the analysis of our results. The relaxation behavior of the specific heat capacity is compared with literature results for other physical quantities and a detailed analysis of the temperature dependence of the relaxation parameters is presented.     

Comparison of collinear and transverse photothermal deflection spectroscopy for trace analysis of pesticides in water

Summary A fiber optic modified photothermal deflection spectrometer (PTDS) was developed and tested for trace analysis of pesticides in water. A UV argon laser beam (=363.8 nm) was delivered to a sample cuvette either directly, or through a multimode optical fiber of 400 m core diameter. The HeNe-probe laser beam was guided to the same sample cuvette by a monomode optical fiber of 5 m core diameter and focussed not only transverse within an angle of 90°, but also collinear within an angle of approximately 0° to the Ar⁺-excitation beam. In transverse dual beam experiments a limit of detection (LOD) of 400 ppt for the pesticide DNOC (4,6-dinitroorthocresol) was achieved. The LODs for 2,4-dinitrophenol, dinoseb and dinosebacetate were 2 ppb, 18 pbb and 6 ppb, respectively. These LODs obtained with the transverse PTDS are up to 2 orders of magnitudes lower than the values taken with the Cary 2400 spectrophotometer. In collinear PTDS experiments with the pesticide dinosebacetate the enhancement factor of the LOD is about 4, when compared to the transverse PTDS using 1×1 cm² diameter sample cuvettes.     

Line sources in absorption spectroscopy

Hollow-cathode tubes and discharge lamps are studied as spectral sources for absorption spectrophotometry. Comparisons are made of monochromatic versus conventional continuous sources with respect to several experimental parameters, particularly the effect of slitwidth. Working curves are shown to indicate the possible advantages of using line sources for narrow band absorption systems.     

Imaged intracavity laser absorption spectroscopy

Using a laser resonator design which supports many high order transverse modes it is possible to enhance a spatial variation (i.e., an image) as well as a spectral variation in absorption of a sample inside the optical cavity of an organic dye laser. This technique also enhances the practical sensitivity of intracavity absorption spectroscopy.     

Transverse photothermal deflection spectroscopy (PDS) applied to thermal diffusiyity measurements

Transverse photothermal deflection spectroscopy(PDS) is applied for the determination of thermal diffusivities of solid surfaces. The theory of PDS is briefly recalled and some approximated analytical formulae concerning the transverse configuration are derived. In materials where the thermal diffusivity is smaller than that of the air, the dependence of the deflection angle on the displacement between pump and probe beams is shown to have a minimum that relates to the thermal diffusivity, thereby allowing its straightforward measurement. Measurements carried out on Al₂O₃ samples with different porosities at room temperature show a good agreement between experiment and theory.

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Zusammenfassung Die transverse photothermische Reflektionsspektroskopie (PDS) wird zur Bestimmung der thermischen Diffusivität von festen Oberflächen herangezogen. Die Theorie der PDS wird kurz dargelegt und einige sich auf die transverse Konfiguration beziehenden analytischen Näherungsgleichungen abgeleitet. Es wird gezeigt, daß bei Materialien mit kleinerer thermischer Diffusivität als Luft die Abhängigkeit des Deflektionswinkels von der Ablenkung zwischen Pumpen- und Probenstrahl ein Minimum aufweist, das mit der thermischen Diffusivität im Zusammenhang steht und somit deren zuverlässige Messung ermöglicht. An Al₂O₃-Proben unterschiedlicher Porosität bei Raumtemperatur ausgeführte Messungen zeigen gute Übereinstimmung von Experiment und Theorie.

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Acetylene weak bands at 2.5 μm from intracavity Cr:ZnSe laser absorption observed with time-resolved Fourier transform spectroscopy

The spectral dynamics of a mid-infrared multimode Cr(2+):ZnSe laser located in a vacuum sealed chamber containing acetylene at low pressure is analyzed by a stepping-mode high-resolution time-resolved Fourier transform interferometer. Doppler-limited absorption spectra of C(2)H(2) in natural isotopic abundance are recorded around 4000 cm(-1) with kilometric absorption path lengths and sensitivities better than 3 10(-8) cm(-1). Two cold bands are newly identified and assigned to the ν(1)+ν(4) (1) and ν(3)+ν(5) (1) transitions of (12)C(13)CH(2). The ν(1)+ν(5) (1) band of (12)C(2)HD and fourteen (12)C(2)H(2) bands are observed, among which for the first time ν(2)+2ν(4) (2)+ν(5) (-1).