RESUMO
We present results of time-dependent quantum mechanics (TDQM) and quasiclassical trajectory (QCT) studies of the excitation function for O(3P) + H2(v = 0-3,j = 0) --> OH + H from threshold to 30 kcal/mol collision energy using benchmark potential energy surfaces [Rogers et al., J. Phys. Chem. A 104, 2308 (2000)]. For H2(v = 0) there is excellent agreement between quantum and classical results. The TDQM results show that the reactive threshold drops from 10 kcal/mol for v = 0 to 6 for v = 1, 5 for v = 2 and 4 for v = 3, suggesting a much slower increase in rate constant with vibrational excitation above v = 1 than below. For H2(v > 0), the classical results are larger than the quantum results by a factor approximately 2 near threshold, but the agreement monotonically improves until they are within approximately 10% near 30 kcal/mol collision energy. We believe these differences arise from stronger vibrational adiabaticity in the quantum dynamics, an effect examined before for this system at lower energies. We have also computed QCT OH(v',j') state-resolved cross sections and angular distributions. The QCT state-resolved OH(v') cross sections peak at the same vibrational quantum number as the H2 reagent. The OH rotational distributions are also quite hot and tend to cluster around high rotational quantum numbers. However, the dynamics seem to dictate a cutoff in the energy going into OH rotation indicating an angular momentum constraint. The state-resolved OH distributions were fit to probability functions based on conventional information theory extended to include an energy gap law for product vibrations.
RESUMO
Near-visible absorption lines of ambient H(2)O vapor and normal and heavy isotopes of O(2) have been measured over atmospheric paths of up to 0.46 km by using two wavelength-modulated, line-locked AlGaAs laser sources with a retroreflector-telescope system. The absolute signal levels agree with theoretical calculations for the O(2) isotopes to within 2%, which is similar to the accuracy with which the column densities were known. Measurements of (16)O(2) linewidths and line strengths were made, and they agree with literature values to within experimental error. The detection sensitivity for (16)O(18)O was found to be 0.1 part in 10(6) atm. km, correspondingto an absorbance sensitivity of 1 × 10(-5). It is concluded that atmospheric trace-gas sensing will be feasible with this apparatus over distances of several kilometers and at levels under 1 part in 10(6).
RESUMO
A new optical hydrogen sensor based on spontaneous Raman scattering of laser light has been designed and constructed for rugged field use. It provides good sensitivity (better than 100 parts in 10(6)), rapid response (several seconds), and the inherent Raman characteristics of linearity and background gas independence of the signal. Efficient light collection and discrimination by using fast optics and a bandpass interference filter compensate for the inefficiency of the Raman-scattering process. A multipass optical cavity with a Herriott-type configuration provides intense illumination from an air-cooled cw gas laser. The observed performance is in good agreement with the theoretical signal and noise level predictions.
RESUMO
The technique of line-locked wavelength modulation with 2f detection is applied to the measurement of water vapor concentration and absorption line parameters by using an 820-nm AlGaAs communications diode laser. Measurements of the 2f signal as a function of the modulation amplitude yield accurate concentrations and line parameters over a pressure range of an order of magnitude and half-widths from 0.02 to 0.15 cm(-1). Usingtwo different spectral lines, we determined concentrations and line parameters with 1% precision, and the absolute accuracy of the line parameters is 3% or better. The results have been used to calculate calibration curves for a diode laser humidity monitor.