Engineering topics
Publications and source records attributed to Wang, C. C..
The vapor pressure of potassium has been measured in absorption using a CW tunable laser and calibrated against the accurate radiative lifetime of the 4s-4p doublet of potassium. An accurate value of 20,850 + or - 30 cal/mol for the heat of vaporization (from the liquid phase) at the melting point was determined.
Oscillator-strength measurements have been calibrated against the radiative lifetime for the 4s-4p transition of potassium. This yields a value of (8.1 + or - 0.5) times 10 to the -21 sq cm for the photoionization cross section at the series limit, and implies a value for the cross-section minimum in good quantitative agreement with that calculated by Seaton (1951).
It is found that the line width of the excitation spectrum for multiphoton ionization is broadened much more severely than the cascade fluorescence originating from the resonant intermediate level. These results derive from the mutual effects of the ionizing and resonating transitions, which are not properly accounted for in perturbative treatments. In general, the ionization line shape can be expressed as the sum of two Lorentzian components, each with different degrees of broadening. This line shape reduces to that of the resonating transition in the limit of vanishing intensities. Moreover, the fluorescence line shape may also exhibit a second component whose amplitude may become important under certain conditions.
The use of a laser-induced fluorescence technique for the sensitive measurement of the atmospheric hydroxyl radical is discussed. Results of laboratory studies of the fluorescence and other spectroscopic properties of OH which allow the calculation of OH concentrations from the returned signals for various altitudes, water vapor contents and temperatures are presented. The experimental setup used for airborne OH measurements is then described, with particular attention given to the use of a telescope for excitation and light collection in a coaxial configuration and the periodic tuning of the exciting radiation necessary to obtain an OH signal in the presence of strong solar and nonresonant fluorescence backgrounds. The best detection limit obtained to date with the system is noted to be about 700,000 OH/cu cm, and it is expected that, with planned improvements in detection and tuning schemes, limits in the neighborhood of 1,000,000 OH/cu cm will be achieved routinely.
The lifetime of the excited state of a atom or molecule is often determined from the rate of fluorescence decay originating as a function of buffer gas pressure, an accurate determination is made of the rates of collision induced transitions away from the excited state. Deconvolution can in principle be employed to resolve fluorescence times shorter than the response times of the system. However, attainable reproducibility and accuracy in actual experiments usually set a limit beyond which no meaningful results are expected. Prudence thus dictates that the results of deconvolution be viewed with extreme caution whenever fluorescence time much shorter than the response of times of the system are indicated.
An absorption technique is described which utilizes a stabilized frequency-doubled tunable dye laser and a long-path White cell with high mirror reflectivities both in the red and UV. In laboratory conditions it has been possible to routinely obtain a detection sensitivity of 3 parts in 1,000,000 over absorption paths less than 1 m in length and a detection sensitivity of approximately 6 parts in 100,000 over an absorption path of the order of 1 km. The latter number corresponds to 3,000,000 OH molecules/cu cm, and therefore the technique should be particularly useful for calibration the fluorescence instrument for OH measurements. However, the presence of atmospheric fluctuations coupled with intensity variation accompanying frequency scanning appears to degrade the detection sensitivity in outdoor ambient conditions, thus making it unlikely that this technique can be employed for direct OH monitoring.
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The homogeneously broadened linewidth of OH due to collisions with water molecules was found to decrease with increasing rotational excitation, and tended to level off to a constant value. This observed dependence is a manifestation of the rotational distribution of the water molecule through rotational transitions in near resonance with those of the OH. The constant value at high rotational excitation reflects the nonresonant contributions to the homogeneous linewidth similar to those due to nonpolar molecules.
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Direct lifetime measurements at pressures up to 25 torr are used to determine the quenching rates for the A 2 Sigma + (v = 0) state of OH due to N2, O2, H2O, and air. The results are found to corroborate quenching values obtained in a similar manner in the millitorr pressure range and show that the quenching cross sections of N2 is pressure independent at least up to 25 torr, that the quenching cross section of O2 is also likely to be pressure independent, and that the quenching values deduced from low-pressure experiments can be safely employed for atmospheric measurements of OH.
In the study described, a single-frequency tunable CW dye laser was used to obtain accurate absorption measurements of the band oscillator strength for various rotational-electronic lines in some transitions of OH. The band oscillator strength is shown to decrease linearly with the energy of rotational excitation. This decrease is attributed exclusively to the lengthening of the internuclear distance due to rotation.
The paper describes an absorption measurement for determining the Gibbs free energy of OH generated in a mixture of water and oxygen vapor. These measurements afford a direct verification of the accuracy of thermochemical data of H2O at high temperatures and pressures. The results indicate that values for the heat capacity of H2O obtained through numerical computations are correct within an experimental uncertainty of 0.15 cal/mole K.
Absorption of OH was measured using a CW tunable laser. Results indicate that this technique, when combined with frequency modulation, promises a sensitivity of 100,000 molecules/cu cm for OH monitoring in the atmosphere.
A simultaneous determination of the rotational and translational temperatures of OH(2 Pi) in a water-vapor discharge is reported. These temperatures were determined by measuring the strength and line shape of the absorption lines in the 2 Pi (v = 0) - 2 Sigma(+) (v = 0) transitions of OH using a CW tunable laser. It was found that the rotational distribution was thermalized, but the corresponding rotational temperature was much lower than the translational temperature. Possible implications of these results are discussed.
By varying the pulsewidth of the output from two dye lasers, it is verified experimentally that the steady-state interference level of OH due to laser-induced dissociation of ozone decreases linearly with decreasing pulsewidth of the exciting radiation. At low pressures, further reduction in the interference level due to the transient nature of OH formation processes was also observed. These results should greatly facilitate measurements of OH concentrations in the atmosphere.
The intensity and pressure dependence of the fluorescence spectrum of OH in the presence of N2 and H2O molecules was studied. Saturation of the absorption transition was observed at low pressures, and the corresponding fluorescence signal was found to vary as the square root of the exciting intensity. This observed dependence agreed with the predicted dependence which took into account the presence of laser modes in the spectrum of the exciting radiation. With full laser power incident, a saturation parameter as high as 3 x 10 to the 5th was observed. The fluorescence spectrum was found to peak at 3145 and at 3090 A, with the relative peak intensities dependent upon gas pressures and upon the particular rotational electronic transition used for excitation. It is concluded that vibrational relaxation of the electronically excited OH due to water vapor in the system plays a dominant role in determining the observed fluorescence spectrum.