Thomas A. Reichardt

Theoretical calculation of line shapes and saturation effects in polarization spectroscopy

The physics of polarization spectroscopy (PS) is investigated by direct numerical integration of the time-dependent density matrix equations. The Zeeman structure of the upper and lower energy levels is included in a multistate formulation of the density matrix equations. The numerical solution of the time-dependent density matrix equations enables us to investigate the effects of strong saturation on PS signal levels and line shapes. Bath levels not directly coupled by the laser radiation are included in the numerical modeling to investigate the effects of collisional rates and different types of collisions on signal levels and line shapes. The effects of Doppler broadening are included by solving the density matrix equations for numerous velocity groups. At low laser power we find that the homogeneously broadened PS line shape is Lorentzian-cubed, as compared to the Lorentzian predicted in several previous low-power analytical solutions. In the low laser power regime, the line-center PS signal is propor...

Collisional dependence of polarization spectroscopy with a picosecond laser

The collisional dependence of polarization spectroscopy (PS) with a picosecond-pulse laser is investigated theoretically with a perturbative treatment and experimentally by probing hydroxyl (OH) in a flow cell with a buffer gas of argon. Using a frequency-doubled distributed-feedback dye laser (DFDL), the PS signal strength is monitored as a function of pressure using a nonsaturating pump beam and a saturating pump beam. The collisional dependence of the PS signal is found to decrease significantly with a saturating pump beam. Increasing the flow-cell pressure by a factor of 50 (from 10 torr to 500 torr), the PS signal strength produced with a nonsaturating pump beam decreases by a factor of 18 while that produced with a saturating pump decreases by only a factor of 3. A third-order perturbative (weak-field) approach is used to develop an analytical expression for the PS signal generated by single-mode, exponentially decaying laser pulses. This expression correctly predicts the experimental results acquir...

Experimental investigation of saturated degenerate four-wave mixing for quantitative concentration measurements.

Degenerate four-wave mixing (DFWM) line shapes and signal intensities are measured experimentally in well-characterized hydrogen-air flames operated over a wide range of equivalence ratios. We use both low (perturbative) and high (saturating) beam intensities in the phase-conjugate geometry. Resonances in the A 2Sigma+ -X 2II (0,0) band of OH are probed with multiaxial-mode laser radiation. The effects of saturation on the line-center signal intensity and the resonance linewidth are investigated. The DFWM signal intensities are used to measure OH number densities in a series of near-adiabatic flames at equivalence ratios ranging from 0.5 to 1.5. Use of saturating pump intensities minimizes the effects of beam absorption, providing more-accurate number density measurements. The saturated DFWM results are in excellent agreement with OH absorption measurements and equilibrium calculations of OH number density. The polarization dependence of the P(1)(2) and R(2)(1) resonances is investigated in both laser intensity regimes. There is a significant change in relative reflectivities for different polarization configurations when saturated.

Experimental investigation of saturated polarization spectroscopy for quantitative concentration measurements

Polarization-spectroscopy (PS) line shapes and signal intensities are measured in well-characterized hydrogen-air flames operated over a wide range of equivalence ratios. We use both low (perturbative) and high (saturating) pump beam intensities in the counterpropagating pump-probe geometry. The effects of saturation on the line-center signal intensity and the resonance linewidth are investigated. The PS signal intensities are used to measure relative OH number densities in a series of near-adiabatic flames at equivalence ratios (phi) ranging from 0.5 to 1.5. The use of saturating pump intensities minimizes the effect of pump beam absorption, providing more accurate number density measurements. When calibrated to the calculated OH concentration in the phi = 0.6 flame, the saturated PS number density measurements probing the P(1)(2) transition are in excellent agreement with OH absorption measurements, equilibrium calculations of OH number density, and previous saturated degenerate four-wave mixing OH number density measurements.

Polarization spectroscopy using short-pulse lasers: Theoretical analysis

The physics of short-pulse polarization spectroscopy (PS) and the diagnostic potential for quantitative measurements of species concentration are investigated by direct numerical integration (DNI) of the time-dependent density matrix equations for a multistate system. The effects of laser power, collision rates, and Doppler broadening on the short-pulse PS signal generation process are investigated by systematically varying these parameters in the numerical calculations. It is found that the use of a short-pulse laser (laser pulse width τL τC), even for a nonsaturating pump beam. For a saturating pump beam, the short-pulse PS signal is found to be nearly independent of collision rate. Increasing the collision rate by a factor of 100 (from 108 to 1010 s−1), the calculated PS signal strength decreases by only a factor of 2 for a 100-ps pump laser at high intensit...

Comparison of Gas Temperatures Measured by Coherent Anti-Stokes Raman Spectroscopy (CARS) of O(2) and N(2).

We investigate the accuracy of temperature measurements by coherent anti-Stokes Raman spectroscopy (CARS) of O(2) and use measurements taken with N(2) CARS and a thermocouple for comparison. Scanning vibrational CARS spectra of O(2) and N(2) were recorded over a broad range of temperatures: between 294 K and 1900 K in air that was heated in a tube furnace and at approximately 2450 K in a fuel-lean CH(4)-O(2)-N(2) flame. Temperatures were derived from least-squares fits of simulated and experimental spectra. Both the fundamental vibrational band and the first hot vibrational band were included in fitting. In the case of the tube furnace, the N(2) and the O(2) CARS temperature measurements agreed to within 3%, and results were similar with the thermocouple; in the flame the agreement was to within 1%. We conclude that, for cases in which O(2) is present in sufficient concentrations ( approximately 10% or greater), the accuracy of O(2) thermometry is comparable with that of N(2).

Resonant degenerate four-wave mixing spectroscopy of transitions with degenerate energy levels: Saturation and polarization effects

The physics of the degenerate four-wave mixing process for resonant transitions between two degenerate energy levels is investigated by direct numerical integration of the time-dependent density matrix equations. The Zeeman structure of the upper and lower energy levels is included in a multistate formulation of the density matrix equations. The inclusion of the Zeeman structure enables the investigation of the degenerate four-wave mixing process for different polarization configurations of the forward pump, backward pump, and probe beams. Saturation curves and lineshapes are calculated for different polarization configurations and for numerous low-J transitions. At low laser intensity, the results of our calculations are in excellent agreement with perturbation theory in terms of the relative intensities of the degenerate four-wave mixing signal for linear polarization configurations. As the laser intensity increases and the resonance starts to saturate, we find in general that the relative degenerate fo...

Frequency-locked, injection-seeded, pulsed narrowband optical parametric generator

A frequency-locked, injection-seeded, pulsed optical parametric generator (OPG) has been developed for short-range infrared differential absorption lidar (DIAL) applications. The periodically poled lithium niobate OPG is pumped by a passively Q-switched Nd:YAG microlaser and is seeded by a distributed feedback (DFB) diode laser. The OPG is designed for DIAL measurement of a narrow R-branch transition of methane at 3.2704 microm. The output of the OPG is a two-pulse sequence with a 100-micros temporal separation between the pulses, where the first pulse is absorbed by methane and the second pulse is not absorbed. The first pulse is actively locked to the methane absorption feature by use of the derivative of the transmission spectrum through a reference cell. Although the device was not optimized for output power, the 3.27-microm OPG output energies of the first and second pulses are 5.5 and 5.9 microJ, respectively, producing 21 mW when operated at 1818 Hz.

Calculation of radiative transition rates for polarized laser radiation

The calculation of laser-induced radiative transition rates for electric-dipole transitions is reviewed. The effects of laser polarization can only be understood by considering the Zeeman structure of energy levels. In particular, the case of laser coupling of degenerate levels is considered by including the Zeeman structure of the upper and lower energy levels. The interaction of the laser radiation with the atomic or molecular resonance is formulated in terms of the density matrix. The electric-dipole matrix elements are written as the product of a scalar quantity, the reduced density matrix element, and a vector quantity that is a function of the angular momentum quantum numbers J and magnetic quantum numbers M for the upper and lower Zeeman states. The calculation of absorption and stimulated emission rates, absorption coefficients, and susceptibilities for the limiting case of an isotropic medium is reviewed. Polarization effects in laser-induced fluorescence are reviewed, and the theoretical framework for the analysis of these effects is developed. The calculation of polarization spectroscopy signals and of polarization effects in resonant four-wave mixing are discussed. The effects of hyperfine structure in diatomic molecules are discussed.

Application of laser photofragmentation-resonance enhanced multiphoton ionization to ion mobility spectrometry

We demonstrate detection of nitro-containing compounds with laser photofragmentation (PF) coupled with resonance enhanced multiphoton ionization (REMPI) and ion mobility spectrometry (IMS). In PF-REMPI, a laser dissociates the parent molecules, producing fragments that can then be ionized by absorption of additional laser photons. The production of these ions strongly depends on the wavelength of laser light, with ion yields corresponding to the absorption spectrum of the fragments [nitric oxide (NO) in the present case]. Combining IMS with PF-REMPI provides further specificity, separating ions according to their mobilities through an atmospheric-pressure drift tube. In this work, we use a pulsed UV laser to examine the characteristics of atmospheric-pressure PF-REMPI, the chemistry occurring in the ionization region and drift tube, and the viability of detecting ions created by both resonance-enhanced and nonresonant ionization. Probing NO in a helium-nitrogen bath, we demonstrate that the detection of ions displays single-shot response to changes in ion generation, with an ion extraction-to-collection efficiency of approximately 12%. We then evaluate the sensitivity and specificity of PF-REMPI/IMS as applied to the detection of both the explosive surrogate 2, 4-dinitrotoluene and the nuisance compound nitrobenzene.