Patrick F. Conforti

Global potential energy surfaces for O(P3)+H2O(A11) collisions

Global analytic potential energy surfaces for O((3)P) + H(2)O((1)A(1)) collisions, including the OH + OH hydrogen abstraction and H + OOH hydrogen elimination channels, are presented. Ab initio electronic structure calculations were performed at the CASSCF + MP2 level with an O(4s3p2d1f)/H(3s2p) one electron basis set. Approximately 10(5) geometries were used to fit the three lowest triplet adiabatic states corresponding to the triply degenerate O((3)P) + H(2)O((1)A(1)) reactants. Transition state theory rate constant and total cross section calculations using classical trajectories to collision energies up to 120 kcal  mol(-1) (∼11 km  s(-1) collision velocity) were performed and show good agreement with experimental data. Flux-velocity contour maps are presented at selected energies for H(2)O collisional excitation, OH + OH, and H + OOH channels to further investigate the dynamics, especially the competition and distinct dynamics of the two reactive channels. There are large differences in the contributions of each of the triplet surfaces to the reactive channels, especially at higher energies. The present surfaces should support quantitative modeling of O((3)P) + H(2)O((1)A(1)) collision processes up to ∼150 kcal  mol(-1).

Long-wave infrared surface reflectance spectra retrieved from Telops Hyper-Cam imagery

Processing long-wave infrared (LWIR) hyperspectral imagery to surface emissivity or reflectance units via atmospheric compensation and temperature-emissivity separation (TES) affords the opportunity to remotely classify and identify solid materials with minimal interference from atmospheric effects. This paper describes an automated atmospheric compensation and TES method, called FLAASH®-IR (Fast Line-of-sight Atmospheric Analysis of Spectral Hypecubes-- Infrared), and its application to ground-to-ground imagery taken with the Telops Inc. Hyper-Cam interferometric hyperspectral imager. The results demonstrate that clean, quantitative surface spectra can be obtained, even with highly reflective (low emissivity) objects such as bare metal and in the presence of some illumination from the surroundings. In particular, the atmospheric compensation process suppresses the spectral features due to atmospheric water vapor and ozone, which are especially prominent in reflected sky radiance.

An accelerated line-by-line option for MODTRAN combining on-the-fly generation of line center absorption within 0.1 cm-1 bins and pre-computed line tails

A Line-By-Line (LBL) option is being developed for MODTRAN6. The motivation for this development is two-fold. Firstly, when MODTRAN is validated against an independent LBL model, it is difficult to isolate the source of discrepancies. One must verify consistency between pressure, temperature and density profiles, between column density calculations, between continuum and particulate data, between spectral convolution methods, and more. Introducing a LBL option directly within MODTRAN will insure common elements for all calculations other than those used to compute molecular transmittances. The second motivation for the LBL upgrade is that it will enable users to compute high spectral resolution transmittances and radiances for the full range of current MODTRAN applications. In particular, introducing the LBL feature into MODTRAN will enable first-principle calculations of scattered radiances, an option that is often not readily available with LBL models. MODTRAN will compute LBL transmittances within one 0.1 cm-1 spectral bin at a time, marching through the full requested band pass. The LBL algorithm will use the highly accurate, pressure- and temperature-dependent MODTRAN Padé approximant fits of the contribution from line tails to define the absorption from all molecular transitions centered more than 0.05 cm-1 from each 0.1 cm-1 spectral bin. The beauty of this approach is that the on-the-fly computations for each 0.1 cm-1 bin will only require explicit LBL summing of transitions centered within a 0.2 cm-1 spectral region. That is, the contribution from the more distant lines will be pre-computed via the Padé approximants. The status of the LBL effort will be presented. This will include initial thermal and solar radiance calculations, validation calculations, and self-validations of the MODTRAN band model against its own LBL calculations.

Collision Dynamics of O(3P) + DMMP Using a Specific Reaction Parameters Potential Form

Starting from previous benchmark CBS-QB3 electronic structure calculations (Conforti, P. F.; Braunstein, M.; Dodd, J. A. J. Phys. Chem. A 2009, 113, 13752), we develop two global potential energy surfaces for O((3)P) + DMMP collisions, using the specific reaction parameters approach. Each surface is simultaneously fit along the three major reaction pathways: hydrogen abstraction, hydrogen elimination, and methyl elimination. We then use these surfaces in classical dynamics simulations and compute reactive cross sections from 4 to 10 km s(-1) collision velocity. We examine the energy disposal and angular distributions of the reactive and nonreactive products. We find that for reactive collisions, an unusually large amount of the initial collision energy is transformed into internal energy. We analyze the nonreactive and reactive product internal energy distributions, many of which fit Boltzmann temperatures up to ~2000 K.

Robust hyperspectral detection with algorithm fusion

Two simple methods are described for fusing the outputs of hyperspectral rare target detection algorithms to achieve more consistent results across a variety of images and objects of interest. The methods are demonstrated with atmospherically corrected (spectral reflectance) visible/near-infrared/shortwave-infrared and long-wavelength infrared hyperspectral imagery using five different detection algorithms that output generalized likelihood ratio decision statistics. Results are presented for nine test cases.

Energetics and Dynamics of the Reactions of O(3P) with Dimethyl Methylphosphonate and Sarin

Electronic structure and molecular dynamics calculations were performed on the reaction systems O((3)P) + sarin and O((3)P) + dimethyl methylphosphonate (DMMP), a sarin simulant. Transition state geometries, energies, and heats of reaction for the major reaction pathways were determined at several levels of theory, including AM1, B3LYP/6-311+G(d,p), and CBS-QB3. The major reaction pathways for both systems are similar and include H-atom abstraction, H-atom elimination, and methyl elimination, in rough order from low to high energy. The H-atom abstraction channels have fairly low barriers (approximately 10 kcal mol(-1)) and are close to thermoneutral, while the other channels have relatively high energy barriers (>40 kcal mol(-1)) and a wide range of reaction enthalpies. We have also found a two-step pathway leading to methyl elimination through O-atom attack on the phosphorus atom for DMMP and sarin. For sarin, the two-step methyl elimination pathway is significantly lower in energy than the single-step pathway. We also present results of O((3)P) + sarin and O((3)P) + DMMP reaction cross sections over a broad range of collision energies (2-10 km s(-1) collision velocities) obtained using the direct dynamics method with an AM1 semiempirical potential. These excitation functions are intended as an approximate guide to future hyperthermal measurements, which to our knowledge have not yet examined either of these systems. The reaction barriers, reaction enthalpies, transition state structures, and excitation functions are generally similar for DMMP and sarin, with some moderate differences for methyl elimination energetics, which indicates DMMP will likely be a good substitute for sarin in many O((3)P) chemical investigations.

Remote sensing of surface emissivity with the telops Hyper-Cam

Processing long-wave infrared (LWIR) hyperspectral imagery to surface spectral emissivity or reflectance units via atmospheric compensation and temperature-emissivity separation (TES) affords the opportunity to remotely classify and identify surface materials with minimal interference from atmospheric effects. This paper describes an automated atmospheric compensation and TES method, called FLAASH-IR (Fast Line-of-sight Atmospheric Analysis of Spectral Hypercubes — Infrared), and its application to airborne imagery taken with the Telops Inc. Hyper-Cam interferometric hyperspectral imager. The results demonstrate good suppression of the atmospheric features due to water vapor and ozone, resulting in quantitative surface spectra, even with highly reflective (low emissivity) objects such as bare metal.

Spectral image destriping using a low-dimensional model

Striping effects, i.e., artifacts that vary systematically with the image column or row, may arise in hyperspectral or multispectral imagery from a variety of sources. One potential source of striping is a physical effect inherent in the measurement, such as a variation in viewing geometry or illumination across the image. More common sources are instrumental artifacts, such as a variation in spectral resolution, wavelength calibration or radiometric calibration, which can result from imperfect corrections for spectral “smile” or detector array nonuniformity. This paper describes a general method of suppressing striping effects in spectral imagery by referencing the image to a spectrally lowdimensional model. The destriping transform for a given column or row is taken to be affine, i.e., specified by a gain and offset. The image cube model is derived from a subset of spectral bands or principal components thereof. The general approach is effective for all types of striping, including broad or narrow, sharp or graduated, and is applicable to radiance data at all optical wavelengths and to reflectance data in the solar (visible through short-wave infrared) wavelength region. Some specific implementations are described, including a method for suppressing effects of viewing angle variation in VNIR-SWIR imagery.

Long-wavelength infrared hyperspectral data "mining" at Cuprite, NV

In recent years long-wavelength infrared (LWIR) hyperspectral imagery has significantly improved in quality and become much more widely available, sparking interest in a variety of applications involving remote sensing of surface composition. This in turn has motivated the development and study of LWIR-focused algorithms for atmospheric retrieval, temperature-emissivity separation (TES) and material detection and identification. In this paper we evaluate some LWIR algorithms for atmospheric retrieval, TES, endmember-finding and rare material detection for their utility in characterizing mineral composition in SEBASS hyperspectral imagery taken near Cuprite, NV. Atmospheric correction results using the In-Scene Atmospheric Correction (ISAC) method are compared with those from the first-principles, MODTRAN©-based FLAASH-IR method. Covariance-whitened endmember-finding methods are observed to be sensitive to image artifacts. However, with clean data and all-natural terrain they can automatically locate and distinguish many minor mineral components, with especially high sensitivity to varieties of calcite. Not surprisingly, the major scene materials, including silicates, are best located using unwhitened techniques. Minerals that we identified in the data include calcite, quartz, alunite and (tentatively) kaolinite.

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.