Jaime Stearns

Identification of vapor-phase chemical warfare agent simulants and rocket fuels using laser-induced breakdown spectroscopy

Application of laser-induced breakdown spectroscopy (LIBS) to the identification of security threats is a growing area of research. This work presents LIBS spectra of vapor-phase chemical warfare agent simulants and typical rocket fuels. A large dataset of spectra was acquired using a variety of gas mixtures and background pressures and processed using partial least squares analysis. The five compounds studied were identified with a 99% success rate by the best method. The temporal behavior of the emission lines as a function of chamber pressure and gas mixture was also investigated, revealing some interesting trends that merit further study.

Conformational Preferences of Gas-Phase Helices: Experiment and Theory Struggle to Agree: The Seven-Residue Peptide Ac-Phe-(Ala)5-Lys-H+

Peptide conformations: IR/UV double-resonance spectroscopy suggested relative energies for four peptide conformations (see figure). These results cannot be reproduced by any of 19 density functional methods.

Hyperthermal atomic oxygen source for near-space simulation experiments

A hyperthermal atomic oxygen (AO) beam facility has been developed to investigate the collisions of high-velocity AO atoms with vapor-phase counterflow. Application of 4.5 kW, 2.4 GHz microwave power in the source chamber creates a continuous discharge in flowing O(2) gas. The O(2) feedstock is introduced into the source chamber in a vortex flow to constrain the plasma to the center region, with the chamber geometry promoting resonant excitation of the TM(011) mode to localize the energy deposition in the vicinity of the aluminum nitride (AlN) expansion nozzle. The approximately 3500 K environment serves to dissociate the O(2), resulting in an effluent consisting of 40% AO by number density. Downstream of the nozzle, a silicon carbide (SiC) skimmer selects the center portion of the discharge effluent, prior to the expansion reaching the first shock front and rethermalizing, creating a beam with a derived 2.5 km s(-1) velocity. Differential pumping of the skimmer chamber, an optional intermediate chamber and reaction chamber maintains a reaction chamber pressure in the mid-10(-6) to mid-10(-5) Torr range. The beam has been characterized with regard to total AO beam flux, O(2) dissociation fraction, and AO spatial profile using time-of-flight mass spectrometric and Kapton-H erosion measurements. A series of reactions AO+C(n)H(2n) (n=2-4) has been studied under single-collision conditions using mass spectrometric product detection, and at higher background pressure detecting dispersed IR emissions from primary and secondary products using a step-scan Michelson interferometer. In a more recent AO crossed-beam experiment, number densities and predicted IR emission intensities have been modeled using the direct simulation Monte Carlo technique. The results have been used to guide the experimental conditions. IR emission intensity predictions are compared to detected signal levels to estimate absolute reaction cross sections.