HCO radical kinetics: Conjunction of laser photolysis and intracavity dye laser spectroscopy

HCO radical at a concentration of about 10¹⁴ cm^?3 is produced by monochromatic laser photolysis of H₂CO with a 0.6 mJ frequency-doubled, flashlamp-pumped dye laser pulse. Intracavity dye laser spectroscopy quantitatively monitors HCO absorbance near 614 nm as a function of delay time between photolysis and probing pulses. Rate constants for HCO + O₂ and HCO + NO are found to be 4.0 ± 0.8 × 10^?12 and 1.45 ± 0.2 × 10^?11 cm³ molecule^?1 sec^?1.     

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.     

Determination of cesium, manganese and terbium by intracavity laser spectroscopy

The statistical characteristics of the intracavity laser spectrometer are investigated by analysis of cesium in aqueous solutions. The error distribution of measurements is normal. The relative standard deviation of the analysis in the middle of the dynamic range is equal to 9.7%. The intracavity spectral analysis was carried out at low contents of cesium, manganese and terbium in aqueous solutions. The limits of detection are: 5 gl^-1 (Cs), 20 gl^-1 (Mn) and 1000 gl^-1 (Tb). Owing to the high spectral resolution of the spectrometer used the hyperfine structure of the thallium absorption line (535.05 nm) was recorded.     

Determination of cesium,manganese and terbium by intracavity laser spectroscopy

The statistical characteristics of the intracavity laser spectrometer are investigated by analysis of cesium in aqueous solutions. The error distribution of measurements is normal. The relative standard deviation of the analysis in the middle of the dynamic range is equal to 9.7%. The intracavity spectral analysis was carried out at low contents of cesium, manganese and terbium in aqueous solutions. The limits of detection are: 5 microg l(-1) (Cs), 20 microg l(-1) (Mn) and 1000 microg l(-1) (Tb). Owing to the high spectral resolution of the spectrometer used the hyperfine structure of the thallium absorption line (535.05 nm) was recorded.     

Discharge-flow kinetics measurements using intracavity laser absorption spectroscopy

Intracavity laser absorption spectroscopy ("ICLAS") has been demonstrated as a feasible detection method for trace species in a discharge flow tube. This implementation has been used to measure the rate of the reaction between atomic hydrogen and NO to form HNO in helium carrier gas. A reaction rate constant of (4.3 +/- 0.4) x 10(-32) cm(6) molecule(-2) s(-1) at 295 K was measured for the reaction H + NO + M --> HNO + M (M = He). The pressure and concentration range enabled by ICLAS detection has allowed us to limit reactive pathways that would inhibit the formation of HNO. The sensitivity of ICLAS, coupled with the versatility of the discharge flow technique, suggests that intracavity absorption spectroscopy will be a useful technique for kinetics measurements on free radicals and other reactive species.     

Electron energy-loss spectroscopy of forbidden transitions to valence and Rydberg states of formaldehyde

The electronic spectrum of formaldehyde has been studied by the technique of electron scattering covering the range of energy loss from 0 to 12 eV with     

Energy transfer and migration in highly forbidden transitions of lanthanide ion doped crystals

Förster–Dexter theory for resonant energy transfer is extended to higher order and applied to explain the rates of energy transfer and migration processes in highly forbidden transitions for some solid-state lanthanide (Ln) ion systems for which experimental results are available. The second-order two-body energy transfer mechanism involves two inter-ion correlated dipole electrostatic interactions, i.e. dipole dipole–dipole dipole (dd–dd) energy transfer, also termed Axe–Axe energy transfer in view of the similarity of the theoretical formalism with that for two-photon transitions. Each of the dipolar transitions consists of a transition from the 4fⁿ configuration to an opposite-parity configuration, taken to be 4fⁿ⁻¹5d. dd–dd energy transfer is a short-range (R⁻¹²) interaction so that it is most important in systems with short donor Ln–acceptor Ln separations. The energy transfer formalism is extended to include spin-forbidden transitions at one or two sites, the so-called Axe–Judd–Pooler (Axe–JP) and JP–JP energy transfer. In some cases the dd–dd mechanism is the dominant energy transfer process, as exemplified herein for energy migration in the ⁵D₀ state of Sm²⁺ in SrF₂, and also in the ⁵D₀ state of Eu³⁺ in Cs₂NaEuCl₆.     

Optimization of detection of atomic absorption lines in intracavity laser spectroscopy

An intracavity laser spectrometer equipped with a graphite furnace electrothermal atomizer and two alternative types of narrow atomic lines detection schemes (high resolution diffraction spectrograph with optical multichannel analyzer or a resonant detector based on a hollow-cathode lamp) is described. Such system was used to determine ultra-trace amounts of lithium and strontium in aqueous solutions. A significant reduction in the measurable absorbance was demonstrated for both elements. Careful optimization of the operating conditions of the detection systems and a comparison of their typical features and advantages were performed.     

Optimization of detection of atomic absorption lines in intracavity laser spectroscopy

An intracavity laser spectrometer equipped with a graphite furnace electrothermal atomizer and two alternative types of narrow atomic lines detection schemes (high resolution diffraction spectrograph with optical multichannel analyzer or a resonant detector based on a hollow-cathode lamp) is described. Such system was used to determine ultra-trace amounts of lithium and strontium in aqueous solutions. A significant reduction in the measurable absorbance was demonstrated for both elements. Careful optimization of the operating conditions of the detection systems and a comparison of their typical features and advantages were performed.     

Cavity-enhanced Raman spectroscopy with optical feedback cw diode lasers for gas phase analysis and spectroscopy

A variant of cavity-enhanced Raman spectroscopy (CERS) is introduced, in which diode laser radiation at 635 nm is coupled into an external linear optical cavity composed of two highly reflective mirrors. Using optical feedback stabilisation, build-up of circulating laser power by 3 orders of magnitude occurs. Strong Raman signals are collected in forward scattering geometry. Gas phase CERS spectra of H(2), air, CH(4) and benzene are recorded to demonstrate the potential for analytical applications and fundamental molecular studies. Noise equivalent limits of detection in the ppm by volume range (1 bar sample) can be achieved with excellent linearity with a 10 mW excitation laser, with sensitivity increasing with laser power and integration time. The apparatus can be operated with battery powered components and can thus be very compact and portable. Possible applications include safety monitoring of hydrogen gas levels, isotope tracer studies (e.g., (14)N/(15)N ratios), observing isotopomers of hydrogen (e.g., radioactive tritium), and simultaneous multi-component gas analysis. CERS has the potential to become a standard method for sensitive gas phase Raman spectroscopy.     

Study of the HNO + HNO and HNO + NO reactions by intracavity laser spectroscopy

Flash photolysis of CH₃CHO and H₂CO in the presence of NO has been investigated by the intracavity laser spectroscopy technique. The decay of HNO formed by the reaction HCO + NO → HNO + CO was studied at NO pressures of 6.8–380 torr. At low NO pressure HNO was found to decay by the reaction HNO + HNO → N₂O + H₂O. The rate constant of this reaction was determined to be k₁ = (1.5 ± 0.8) × 10^?15 cm³/s. At high NO pressure the reaction HNO + NO → products was more important, and its rate constant was measured to be k₂ = (5 ± 1.5) × 10^?19 cm³/s. NO₂ was detected as one of the products of this reaction. Alternative mechanisms for this reaction are discussed.     

Cavity ring-down spectroscopy measurement of single aerosol particle extinction. II. Extinction of light by an aerosol particle in an optical cavity excited by a cw laser

The authors present an analytical derivation of the scattered power from a spherical, homogeneous, nonabsorbing particle in a plane standing wave. The scattered power changes significantly with the position of the particle with respect to the peaks and nodes of the standing wave, even for particles whose diameters are many times the wavelength of the light. The analysis is applicable to continuous-wave cavity ring-down spectroscopy on aerosol particles, and the structure of the standing wave is expected to affect both the measured ring-down time and the shape of the ring-down trace. The dependence of the extinction on the phase of the standing wave at the location of the particle is captured in a parameter zeta which connects the current treatment to standard Mie scattering theory. Methods for calculating zeta are presented.     

Saturation spectroscopy of NH2 using a CW dye laser

Hyperfine structure in the electronic spectrum of NH₂ has been resolved using the technique of intermodulated fluorescence with CW dye laser excitation. From the observed spacings values for the ¹⁴N Fermi contact and dipole-dipole coupling terms have been estimated for both the ground state and the Π(0,10,0) vibrational level of the à ²A₁ excited electronic state.     

Variational principle for the intensity of forbidden transitions

A new variational principle for the probability of forbidden transitions is derived. Upper and lower bounds for the corresponding matrix element are given.     

Analytical applications of laser moding caused by intracavity absorption

A continuous CO₂ laser with a reflecting mirror can operate at several wavelengths simultaneously. If an organic vapor is introduced into a separate cavity in the laser optical path, the laser will sometimes mode rapidly causing some lasing lines to diminish to zero and others to become enhanced; this has been observed even for very low amounts (10^-5 g) of organic gases. Laser intercavity absorption spectroscopy depends on overlap of a vibrational—rotational line of a sample with a laser transition line. The absorption by the sample greatly affects the laser wavetrain at that particular wavelength and interferes with the lasing action. The technique is not based on Beer's law, and the detection limits observed are orders of magnitude better than those of conventional infrared absorption spectroscopy. Two laser systems were used and various organic gases were studied. When a totally reflecting mirror which permitted free moding was used, the detection limits found were 0.14 μg, 0.95 μg and 0.60 μg for vinyl chloride, propylene, and ethylene, respectively. When a grating was used as the rear cavity optics restricting the wavelengths of the laser lines, the detection limits were 140 μg, 94 μg, 63 μg and 0.26 μg for vinyl chloride, propylene. ethylene and ethyl chloride, respectively.     

Measurement of transmission properties of optical fibers for telecommunications by FT-IR spectroscopy

The transmission properties of optical fibers are measured with a modified commercial Fourier transform spectrometer. Examples for spectral attenuation loss measurements are given for silica fibers, fibers of PMMA, and those of zirkonium fluoride.     

Phase control of the competition between electronic transitions in a solvated laser dye

Excited state population can be manipulated by resonant chirped laser pulses through pump–dump processes. We investigate these processes in the laser dye LD690 as a function of wavelength by monitoring the saturated absorption of chirped ultrafast pulses. The resulting nonlinear absorption spectrum becomes increasingly complex as the pulse is tuned to shorter wavelengths. However, fluorescence measurements indicate that the excited state population depends weakly on chirp when the pump wavelength is far from the lowest order electronic transition. Using a learning algorithm and closed-loop control, we find nonlinear chirp parameters that optimize features in the transmission spectrum. The results are discussed in terms of competition between excited state absorption and stimulated resonant Raman scattering.     

The Pt2 (1,0) band of System VI in the near infrared by intracavity laser absorption spectroscopy

Intracavity laser absorption spectroscopy has been used to record rotationally resolved electronic spectra of Pt(2) in the near infrared. The metal dimers were created using a 50 mm-long, platinum-lined hollow cathode plasma discharge. The observed transition at 12?937 cm(-1) is identified as the (1,0) band of System VI, with state symmetries Ω = 0 - X Ω = 0.     

Photoluminescent mechanism of a proton-transfer laser dye in highly doped polymer films

Photoluminescent properties in thin films of the proton-transfer laser dye, 2-(2-hydroxyphenyl)benzothiazole (HBT) were investigated, when it was doped into hole-transport polymer, poly(N-vinylcarbazole) and when it was codoped with hole-transport small molecule, N,N′-di(m-tolyl)-N,N′-diphenylbenzidine (TPD) into polystyrene. The more the doping concentration of HBT was raised up to about 40 wt%, the more its photoluminescent intensity was enhanced without showing excimer or exciplex emissions. The mechanism for such phenomena was discussed in connection with the excited-state intramolecular proton-transfer reaction of HBT.     

Conventional and dye laser optical spectra of zinc porphin in anthracene

Conventional polarized optical absorption spectra and fluorescence spectra of single crystal and polycrystalline samples of zinc porphin in anthracene have been obtained at 4.2 K. Narrow band excitation of fluorescence using a tunable dye laser was used for site selection to eliminate ambiguities due to impurities and multiple sites. The spectra are compared to those of zinc porphin in a different aromatic host (triphenylene) and in n-octane. Some of the vibronic energies are assigned to calculated vibrations of a similar metalloporphin, copper porphin.