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The kinetics of MgO + + CH 4 was studied experimentally using the variable ion source, temperature adjustable selected ion flow tube (VISTA-SIFT) apparatus from 300 − 600 K and computationally by running and analyzing reactive atomistic simula- tions. Rate coefficients and product branching fractions were determined as a function of temperature. The reaction proceeded with a rate of k = 5 . 9 ± 1 . 5 × 10 − 10 ( T/ 300 K) − 0 . 5 ± 0 . 2 cm 3 s − 1 . MgOH + was the dominant product at all temperatures, but Mg + , the co-product of oxygen-atom transfer to form methanol, was observed with a product branching fraction of 0 . 08 ± 0 . 03( T/ 300 K) − 0 . 8 ± 0 . 7 . Reactive molecular dynamics simulations using a reactive force field, as well as a neural network trained on thousands of structures yield rate coefficients about one order of magnitude lower. This underestimation of the rates is traced back to the multireference character of the transition state [MgOCH 4 ] + . Statistical modeling of the temperature-dependent kinetics provides further insight into the reactive potential surface. The rate limiting step was found to be consistent with a four-centered activation of the C-H bond, consistent with previous calculations. The product branching was modeled as a competition between dissociation of an insertion intermediate directly after the rate- limiting transition state, and traversing a transition state corresponding to a methyl migration leading to a Mg-CH 3 OH + complex, though only if this transition state is stabilized significantly relative to the dissociated MgOH + + CH 3 product channel. An alternative non-statistical mechanism is discussed, whereby a post-transition state bifurcation in the potential surface could allow the reaction to proceed directly from the four-centered TS to the Mg-CH 3 OH + complex thereby allowing a more robust competition between the product channels .

Coherent microwave Rayleigh scattering for detection resonance-enhanced multiphoton ionization (radar REh^I) has been developed for trace species in air, atomic and radicals in hydrocarbon flames, plasma parameters, and semiconductor inspection in the past decade.

We present 300 K rate constants for the ion-ion reactions of O + a n d N + with the atomic halide anions: C l - , B r - , a n d I - measured using a flowing afterglow – Langmuir probe apparatus. All six rate constants were > 1 × 10 - 8 c m 3 s - 1 , larger than those typical for atomic ion – atomic ion reactions, approaching the rate constants of more complex ion-ion systems. Evaluation of literature atomic ion – atomic ion rate constants shows variation over orders of magnitude, but limited to below the expected value for a polyatomic ion-ion reaction of the same reduced mass, fitting into an expected physical picture. Unlike for polyatomic systems, estimation of rate constant for atomic ion – atomic ion reaction rates by simple means does not seem effective.

Rate constants for dissociative electron attachment to N2O yielding O− have been measured as a function of temperature from 400 K to 1000 K. Detailed modeling of kinetics was needed to derive the rate constants at temperatures of 700 K and higher. In the 400 K–600 K range, upper limits are given. The data from 700 K to 1000 K follow the Arrhenius equation behavior described by 2.4 × 10−8 e−0.288 eV/kT cm3 s−1. The activation energy derived from the Arrhenius plot is equal to the endothermicity of the reaction. However, calculations at the CCSD(T)/complete basis set level suggest that the lowest energy crossing between the neutral and anion surfaces lies 0.6 eV above the N2O equilibrium geometry and 0.3 eV above the endothermicity of the dissociative attachment. Kinetic modeling under this assumption is in modest agreement with the experimental data. The data are best explained by attachment occurring below the lowest energy crossing of the neutral and valence anion surfaces via vibrational Feshbach resonances.

Rate constants for the reactions of C+ + Cl-, Br-, and I- were measured at 300 K using the variable electron and neutral density electron attachment mass spectrometry technique in a flowing afterglow Langmuir probe apparatus. Upper bounds of

In this work, coherent microwave Rayleigh scattering for the detection of resonance-enhanced multiphoton ionization (Radar REMPI) was used for the measurement of atomic oxygen in a nonequilibrium pulsed plasma discharge. Specifically, the detection of atomic oxygen is demonstrated in a pulsed discharge at 100 Torr in a molecular oxygen and helium gas mixture. REMPI was conducted using Nd:YAG pumped dye radiation at 618.9 nm mixed with the Nd:YAG 355 nm radiation, generating 225.6 nm laser light, of which two photons match the energy of the 2P33p(3P) electronically excited intermediate state of atomic oxygen. A third photon from the laser source then readily ionizes the atom in the 2 + 1 photon REMPI scheme. The Radar REMPI results are compared to two-photon absorption laser-induced fluorescence measurements from the literature, which shows reasonable agreement.In this work, coherent microwave Rayleigh scattering for the detection of resonance-enhanced multiphoton ionization (Radar REMPI) was used for the measurement of atomic oxygen in a nonequilibrium pulsed plasma discharge. Specifically, the detection of atomic oxygen is demonstrated in a pulsed discharge at 100 Torr in a molecular oxygen and helium gas mixture. REMPI was conducted using Nd:YAG pumped dye radiation at 618.9 nm mixed with the Nd:YAG 355 nm radiation, generating 225.6 nm laser light, of which two photons match the energy of the 2P33p(3P) electronically excited intermediate state of atomic oxygen. A third photon from the laser source then readily ionizes the atom in the 2 + 1 photon REMPI scheme. The Radar REMPI results are compared to two-photon absorption laser-induced fluorescence measurements from the literature, which shows reasonable agreement.

A digital holography (DH) surface erosion/deposition diagnostic is being developed for 3D imaging of plasma facing component surfaces in situ and in real time. Digital holography is a technique that utilizes lasers reflected from a material surface to form an interferogram, which carries information about the topology of the surface when reconstructed. As described in this paper, dual CO2 lasers at 9.271 and 9.250 μm wavelengths illuminate the interrogated surface (at a distance of ∼1 m) in a region of ∼1 cm × 1 cm. The surface feature resolution is ∼0.1 mm in the plane of the surface, and the depth resolution ranges from ∼0.0001 to ∼2 mm perpendicular to the surface. The depth resolution lower limit is set by single-laser and detector optical limitations, while the upper limit is determined by 2π phase ambiguity of the dual-laser synthetic wavelength. Measurements have been made "on the bench" to characterize the single-laser and dual-laser DH configurations utilizing standard resolution targets and material targets that were previously exposed to high flux plasmas in either the Prototype Material Plasma Exposure eXperiment (Proto-MPEX) or the electro-thermal (ET) arc source. Typical DH measurements were made with 0.03 ms integration with an IR camera that can be framed at rates approaching 1.5 kHz. The DH diagnostic system is progressing toward in situ measurements of plasma erosion/deposition either on Proto-MPEX or the ET arc source.

Significant reduction of the breakdown threshold in a DC microdischarge via seeding metal nanoparticles has been demonstrated. Compared to standard Paschen curves in dry air, reductions in the breakdown voltage of 5% to 25% were obtained for PD values (the product of pressure and electrode gap distance) ranging from 20 to 40 Torr-cm by seeding aluminum and iron nanoparticles with mean sizes of 75 nm and 80 nm, respectively. No secondary energy source was required to achieve this breakdown threshold reduction. From high-speed chemiluminescence imaging of the discharge evolution, breakdown was shown to be initiated at reduced voltages. Following breakdown, the increase in temperature ignited some of the nanoparticles near the cathode. Results suggest that possible charging of the nanoparticles within the gap may reduce the effective transient distance, leading to the threshold reduction.

In this work, we present findings of significant reduction of the breakdown threshold in a DC microdischarge via seeding metal nanoparticles. Reductions in the breakdown voltage were found to be between 5 to 25% for PD values (the product of pressure and electrode gap distance) of 20 to 40 Torr-cm. These reductions were achieved be seeding aluminum and iron nanoparticles with mean diameters of 75 and 80 nm, respectively. This technique required no secondary energy source to achieve this breakdown threshold reduction. Through high-speed chemiluminescence imaging of the discharge evolution it was found that the increase in temperature following breakdown ignited some of the nanoparticles near the cathode. It is postulated that the breakdown threshold reduction is achieved by an effective reduction in the electrode gap distance due charging of the nanoparticles.

A laser-ignition (LI) method is presented that utilizes a high-repetition-rate (HRR) nanosecond laser to reduce minimal ignition energies of individual pulses by ∼10 times while maintaining comparable total energies. The most common LI employs a single nanosecond-laser pulse with energies on the order of tens of millijoules to ignite combustible gaseous mixtures. Because of the requirements of high energy per pulse, fiber coupling of traditional LI systems is difficult to implement in real-world systems with limited optical access. The HRR LI method demonstrated here has an order of magnitude lower per-pulse energy requirement than the traditional single-pulse LI technique, potentially allowing delivery through standard commercial optical fibers. Additionally, the HRR LI approach significantly increases the ignition probability of lean combustible mixtures in high-speed flows while maintaining low individual pulse energies.

Here we report nonintrusive local rotational temperature measurements of molecular oxygen, based on coherent microwave scattering (radar) from resonance-enhanced multiphoton ionization (REMPI) in room air and hydrogen/air flames. Analyses of the rotational line strengths of the two-photon molecular oxygen C(3)Π(v=2)←X(3)Σ(v'=0) transition have been used to determine the hyperfine rotational state distribution of the ground X(3)Σ(v'=0) state. Rotationally resolved 2+1 REMPI spectra of the molecular oxygen C(3)Π(v=2)←X(3)Σ(v'=0) transition at different temperatures were obtained experimentally by radar REMPI. Rotational temperatures have been determined from the resulting Boltzmann plots. The measurements in general had an accuracy of ~±60 K in the hydrogen/air flames at various equivalence ratios. Discussions about the decreased accuracy for the temperature measurement at elevated temperatures have been presented.

In this paper phenomena seen in microwave scattering experiements from a laser-induced plasma in atmospheric air will be explained via Mie scattering theory. The relative transparency of the laser-induced plasma at microwave frequency is shown to lead to a transition from coherent Rayleigh scattering to Mie scattering. A sharp increase in conductivity during the avalanche ionization phase of the spark evolution alters the microwave penetration from total transparency to partial shielding. Temporal and polar scatterings plots will be presented to show the effects of the transition from Rayleigh scattering to Mie scattering and change in transparency.