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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Competing effects of electronic and nuclear energy loss on microstructural evolution in ionic-covalent materials

Ever increasing energy needs have raised the demands for advanced fuels and cladding materials that withstand the extreme radiation environments with improved accident tolerance over a long period of time. Ceria (CeO2) is a well known ionic conductor that is isostructural with urania and plutonia-based nuclear fuels. In the context of nuclear fuels, immobilization and transmutation of actinides, CeO2 is a model system for radiation effect studies. Covalent silicon carbide (SiC) is a candidate for use as structural material in fusion, cladding material for fission reactors, and an inert matrix for the transmutation of plutonium and other radioactive actinides. Understanding microstructural change of these ionic-covalent materials to irradiation is important for advanced nuclear energy systems. While displacements from nuclear energy loss may be the primary contribution to damage accumulation in a crystalline matrix and a driving force for the grain boundary evolution in nanostructured materials, local non-equilibrium disorder and excitation through electronic energy loss may, however, produce additional damage or anneal pre-existing defects. At intermediate transit energies where electronic and nuclear energy losses are both significant, synergistic, additive or competitive processes may evolve that affect the dynamic response of materials to irradiation. The response of crystalline and nanostructured CeO2 and SiC to ion irradiation are studied under different nuclear and electronic stopping powers to describe some general material response in this transit energy regime. Although fast radiation-induced grain growth in CeO2 is evident with no phase transformation, different fluence and dose dependence on the growth rate is observed under Si and Au irradiations. While grain shrinkage and amorphization are observed in the nano-engineered 3C SiC with a high-density of stacking faults embedded in nanosize columnar grains, significantly enhanced radiation resistance is attributed to stacking faults that promote efficient point defect annihilation. Moreover, competing effects of electronic and nuclear energy loss on the damage accumulation and annihilation are observed in crystalline 4H-SiC. Systematic experiments and simulation effort are needed to understand the competitive or synergistic effects.

36 MATERIALS SCIENCE↗
DOE OSTI2018

The role of defects in Fe(II) – goethite electron transfer

Despite accumulating experimental evidence for Fe(II)-Fe(III) oxide electron transfer, computational chemical calculations suggest that oxidation of sorbed Fe(II) is not energetically feasible unless defects are present. Here we used isotope specific 57Fe Mössbauer spectroscopy to investigate whether Fe(II)-goethite electron transfer is influenced by defects. Specifically, we heated the mineral to try to anneal the goethite surface and ground goethite to try to create defects. We found that heating goethite results in less oxidation of sorbed Fe(II) by goethite. When goethite was re-ground after heating, electron transfer was partially restored. X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) of heated and ground goethite confirm that heating and grinding alter the surface structure of the goethite. We propose that the heating process annealed the surface and decreased the number of sites where electron transfer could occur. Our experimental findings suggest that surface defects play an important role in Fe(II)-goethite electron transfer as suggested by computational calculations. Our finding that defects influence heterogeneous Fe(II)-goethite electron transfer has important implications for Fe(II) driven recrystallization of Fe oxides, as well as X and Y.

Notini, Luiza↗
DOE OSTI2016

Influence of Copper Oxidation State on the Bonding and Electronic Structure of Cobalt-Copper Complexes

Heterobimetallic complexes that pair cobalt and copper were synthesized and characterized by a suite of physical methods, including X-ray diffraction, X-ray anomalous scattering, cyclic voltammetry, magnetometry, electronic absorption spectroscopy, electron paramagnetic resonance, and quantum chemical methods. Both Cu(II) and Cu(I) reagents were independently added to a Co(II) metalloligand to provide (py 3 tren)CoCuCl (1-Cl) and (py 3 tren)CoCu(CH 3 CN) (2-CH 3 CN), respectively, where py3tren is the triply deprotonated form of N,N,N-tris(2-(2-pyridylamino)ethyl)amine. Complex 2-CH 3 CN can lose the acetonitrile ligand to generate a coordination polymer consistent with the formula “(py3tren)CoCu” (2). One-electron chemical oxidation of 2-CH 3 CN with AgOTf generated (py 3 tren)CoCuOTf (1-OTf). The Cu(II)/Cu(I) redox couple for 1-OTf and 2-CH 3 CN is reversible at -0.56 and -0.33 V vs Fc + /Fc, respectively. The copper oxidation state impacts the electronic structure of the heterobimetallic core, as well as the nature of the Co–Cu interaction. Quantum chemical calculations showed modest electron delocalization in the (CoCu) +4 state via a Co–Cu σ bond that is weakened by partial population of the Co–Cu σ antibonding orbital. By contrast, no covalent Co–Cu bonding is predicted for the (CoCu) +3 analogue, and the d-electrons are fully localized at individual metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Two-dimensional vibrational-electronic spectroscopy

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (ν{sub CN}) and either a ligand-to-metal charge transfer transition ([Fe{sup III}(CN){sub 6}]{sup 3−} dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN){sub 5}Fe{sup II}CNRu{sup III}(NH{sub 3}){sub 5}]{sup −} dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific ν{sub CN} modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Experimental determination of electron attenuation lengths in complex materials by means of epitaxial film growth: advantages and challenges

Accurate electron attenuation lengths are of critical importance in using electron spectroscopic methods to quantitatively characterize complex materials. Here we show that analysis of core-level and valence-band x-ray photoelectron spectra excited with monochromatic AlK? x-rays from the substrate and measured as a function of film thickness can be used to determine electron attenuation lengths in epitaxial SrTiO3 films on Ge(001). Closely lattice-matched epitaxial heterojunctions are ideal systems for determining attenuation lengths provided the films grow in a layer-by-layer fashion, leading to atomically flat surfaces, and the buried interfaces are atomically abrupt. In principle, either the rate of attenuation of substrate peak intensities or the rate of increase of film peak intensities can be used for this purpose. However, we find that structural nonuniformities in the films reduce the accuracy of electron attenuation lengths determined from photoelectrons that originate within the films. A more reliable source of information is found in photoelectrons from the substrate which traverse the film. By using the energy dependence of calculated electron attenuation lengths from the NIST database in combination with Ge 3d core and Ge-derived valence band intensities, we determine electron attenuation length as a function of kinetic energy for SrTiO3.

Chambers, Scott A.↗
DOE OSTI2014

Correlation between energy deposition and molecular damage from Auger electrons: A case study of ultra-low energy (5–18 eV) electron interactions with DNA

Purpose: The present study introduces a new method to establish a direct correlation between biologically related physical parameters (i.e., stopping and damaging cross sections, respectively) for an Auger-electron emitting radionuclide decaying within a target molecule (e.g., DNA), so as to evaluate the efficacy of the radionuclide at the molecular level. These parameters can be applied to the dosimetry of Auger electrons and the quantification of their biological effects, which are the main criteria to assess the therapeutic efficacy of Auger-electron emitting radionuclides. Methods: Absorbed dose and stopping cross section for the Auger electrons of 5–18 eV emitted by{sup 125}I within DNA were determined by developing a nanodosimetric model. The molecular damages induced by these Auger electrons were investigated by measuring damaging cross section, including that for the formation of DNA single- and double-strand breaks. Nanoscale films of pure plasmid DNA were prepared via the freeze-drying technique and subsequently irradiated with low-energy electrons at various fluences. The damaging cross sections were determined by employing a molecular survival model to the measured exposure–response curves for induction of DNA strand breaks. Results: For a single decay of{sup 125}I within DNA, the Auger electrons of 5–18 eV deposit the energies of 12.1 and 9.1 eV within a 4.2-nm{sup 3} volume of a hydrated or dry DNA, which results in the absorbed doses of 270 and 210 kGy, respectively. DNA bases have a major contribution to the deposited energies. Ten-electronvolt and high linear energy transfer 100-eV electrons have a similar cross section for the formation of DNA double-strand break, while 100-eV electrons are twice as efficient as 10 eV in the induction of single-strand break. Conclusions: Ultra-low-energy electrons (<18 eV) substantially contribute to the absorbed dose and to the molecular damage from Auger-electron emitting radionuclides; hence, they should be considered in the dosimetry calculation of such radionuclides. Moreover, absorbed dose is not an appropriate physical parameter for nanodosimetry. Instead, stopping cross section, which describes the probability of energy deposition in a target molecule can be an appropriate nanodosimetric parameter. The stopping cross section is correlated with a damaging cross section (e.g., cross section for the double-strand break formation) to quantify the number of each specific lesion in a target molecule for each nuclear decay of a single Auger-electron emitting radionuclide.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
NASA NTRS1995

Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also, the average electron temperature is expected to be between 10,000 and 20,000 K. Thus only data for low energy electrons are relevant to the model.

Huo, Winifred M.↗
DOE OSTI2011

Electron emission from single-electron capture with simultaneous single-ionization reactions in 30-keV/u He{sup 2+}-on-argon collisions

Electron emission from the single-electron capture with simultaneous single ionization in 30 keV/u He{sup 2+} on argon was investigated using a reaction microscope, providing the electron energy spectra and momentum distributions. Intensive peaks for electrons with near-zero kinetic energies have been observed. It is demonstrated that mechanisms contributing to the electron emission include direct transfer ionization (DTI), double-electron capture with autoionization (DECA), and single-electron capture with autoionization (SECA) of target. Comparison of resonance energies shows that Ar{sup +} ions in SECA decay mainly through the 3s3p{sup 5}3d states by emitting Auger electrons, and He** in DECA decay through the 2l2l' states. The dependence of electron emission on the transverse momentum exchange has been studied. In the transfer ionization channel studied here, the DTI process dominates the electron emission, and no saddle point electron mechanism has been found.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2011

Paramagnetic defects in electron-irradiated yttria-stabilized zirconia: Effect of yttria content

We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. It is concluded that F+-type centres might be actually oxygen divacancies (F2+-type centres). Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 ± 1 eV with subsequent defect re-arrangement.

colour centres↗
DOE OSTI2012

Existence domains of arbitrary amplitude nonlinear structures in two-electron temperature space plasmas. II. High-frequency electron-acoustic solitons

A three-component plasma model composed of ions, cool electrons, and hot electrons is adopted to investigate the existence of large amplitude electron-acoustic solitons not only for the model for which inertia and pressure are retained for all plasma species which are assumed to be adiabatic but also neglecting inertial effects of the hot electrons. Using the Sagdeev potential formalism, the Mach number ranges supporting the existence of large amplitude electron-acoustic solitons are presented. The limitations on the attainable amplitudes of electron-acoustic solitons having negative potentials are attributed to a number of different physical reasons, such as the number density of either the cool electrons or hot electrons ceases to be real valued beyond the upper Mach number limit, or, alternatively, a negative potential double layer occurs. Electron-acoustic solitons having positive potentials are found to be supported only if inertial effects of the hot electrons are retained and these are found to be limited only by positive potential double layers.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2013

Precision electroweak studies using parity violation in electron scattering

The nature of new neutral-current interactions can be revealed at the low-energy precision frontier, where studies of parity-violation in electron scattering will complement the energy-frontier studies at the LHC. Measurements of the parity-violating observable A{sub PV} - the cross-section asymmetry in the scattering of longitudinally polarized electrons from an unpolarized target - are sensitive to possible contact interactions from new physics at multi-TeV mass scales. The 12 GeV upgrade at JLab and a new, high-intensity beam at Mainz offer opportunities for significant improvements in measurements of electron-electron and electron-quark parity-violating interactions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2016

Physical mechanism causing rapid changes in ultrarelativistic electron pitch angle distributions right after a shock arrival: Evaluation of an electron dropout event: Drift Shell Splitting on the Dayside

Three mechanisms have been proposed to explain relativistic electron flux depletions (dropouts) in the Earth's outer radiation belt during storm times: adiabatic expansion of electron drift shells due to a decrease in magnetic field strength, magnetopause shadowing and subsequent outward radial diffusion, and precipitation into the atmosphere (driven by EMIC wave scattering). Which mechanism predominates in causing electron dropouts commonly observed in the outer radiation belt is still debatable. In the present study, we evaluate the physical mechanism that may be primarily responsible for causing the sudden change in relativistic electron pitch angle distributions during a dropout event observed by Van Allen Probes during the main phase of the 27 February 2014 storm. During this event, the phase space density of ultrarelativistic (>1MeV) electrons was depleted by more than 1 order of magnitude over the entire radial extent of the outer radiation belt (3 < L* < 5) in less than 6 h after the passage of an interplanetary shock. We model the electron pitch angle distribution under a compressed magnetic field topology based on actual solar wind conditions. Although these ultrarelativistic electrons exhibit highly anisotropic (peaked in 90°), energy-dependent pitch angle distributions, which appear to be associated with the typical EMIC wave scattering, comparison of the modeled electron distribution to electron measurements indicates that drift shell splitting is responsible for this rapid change in electron pitch angle distributions. This further indicates that magnetopause loss is the predominant cause of the electron dropout right after the shock arrival.

58 GEOSCIENCES↗
DOE OSTI2016

Electron Accelerator Shielding Design of KIPT Neutron Source Facility

The Argonne National Laboratory of the United States and the Kharkov Institute of Physics and Technology of the Ukraine have been collaborating on the design, development and construction of a neutron source facility at Kharkov Institute of Physics and Technology utilizing an electron-accelerator-driven subcritical assembly. The electron beam power is 100 kW using 100-MeV electrons. The facility was designed to perform basic and applied nuclear research, produce medical isotopes, and train nuclear specialists. The biological shield of the accelerator building was designed to reduce the biological dose to less than 5.0e-03 mSv/h during operation. The main source of the biological dose for the accelerator building is the photons and neutrons generated from different interactions of leaked electrons from the electron gun and the accelerator sections with the surrounding components and materials. The Monte Carlo N-particle extended code (MCNPX) was used for the shielding calculations because of its capability to perform electron-, photon-, and neutron-coupled transport simulations. The photon dose was tallied using the MCNPX calculation, starting with the leaked electrons. However, it is difficult to accurately tally the neutron dose directly from the leaked electrons. The neutron yield per electron from the interactions with the surrounding components is very small, similar to 0.01 neutron for 100-MeV electron and even smaller for lower-energy electrons. This causes difficulties for the Monte Carlo analyses and consumes tremendous computation resources for tallying the neutron dose outside the shield boundary with an acceptable accuracy. To avoid these difficulties, the SOURCE and TALLYX user subroutines of MCNPX were utilized for this study. The generated neutrons were banked, together with all related parameters, for a subsequent MCNPX calculation to obtain the neutron dose. The weight windows variance reduction technique was also utilized for both neutron and photon dose calculations. Two shielding materials, heavy concrete and ordinary concrete, were considered for the shield design. The main goal is to maintain the total dose outside the shield boundary less than 5.0e-03 mSv/h during operation. The shield configuration and parameters of the accelerator building were determined and are presented in this paper. Copyright (C) 2016, Published by Elsevier Korea LLC on behalf of Korean Nuclear Society.

43 PARTICLE ACCELERATORS↗
DOE OSTI2015

ELECTRON HEATING BY THE ION CYCLOTRON INSTABILITY IN COLLISIONLESS ACCRETION FLOWS. I. COMPRESSION-DRIVEN INSTABILITIES AND THE ELECTRON HEATING MECHANISM

In systems accreting well below the Eddington rate, such as the central black hole in the Milky Way (Sgr A*), the plasma in the innermost regions of the disk is believed to be collisionless and have two temperatures, with the ions substantially hotter than the electrons. However, whether a collisionless faster-than-Coulomb energy transfer mechanism exists in two-temperature accretion flows is still an open question. We study the physics of electron heating during the growth of ion velocity-space instabilities by means of multidimensional, fully kinetic, particle-in-cell (PIC) simulations. A background large-scale compression—embedded in a novel form of the PIC equations—continuously amplifies the field. This constantly drives a pressure anisotropy P > P {sub ∥} because of the adiabatic invariance of the particle magnetic moments. We find that, for ion plasma beta values β{sub 0i} ∼ 5-30 appropriate for the midplane of low-luminosity accretion flows (here, β{sub 0i} is the ratio of ion thermal pressure to magnetic pressure), mirror modes dominate if the electron-to-proton temperature ratio is T {sub 0e}/T {sub 0i} ≳ 0.2, whereas for T {sub 0e}/T {sub 0i} ≲ 0.2 the ion cyclotron instability triggers the growth of strong Alfvén-like waves, which pitch-angle scatter the ions to maintain marginal stability. We develop an analytical model of electron heating during the growth of the ion cyclotron instability, which we validate with PIC simulations. We find that for cold electrons (β{sub 0e} ≲ 2 m{sub e} /m{sub i} , where β{sub 0e} is the ratio of electron thermal pressure to magnetic pressure), the electron energy gain is controlled by the magnitude of the E-cross-B velocity induced by the ion cyclotron waves. This term is independent of the initial electron temperature, so it provides a solid energy floor even for electrons starting with extremely low temperatures. On the other hand, the electron energy gain for β{sub 0e} ≳ 2 m{sub e} /m{sub i} —governed by the conservation of the particle magnetic moment in the growing fields of the instability—is proportional to the initial electron temperature, and it scales with the magnetic energy of ion cyclotron waves. Our results have implications for two-temperature accretion flows as well as for solar wind and intracluster plasmas.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2011

X-ray Emission from Electron Betatron Motion in a Laser-Plasma Accelerator

Single-shot x-ray spectra from electron bunches produced by a laser-plasma wakefield accelerator (LPA) were measured using a photon-counting single-shot pixelated Silicon-based detector [3], providing for the first time direct spectra without assumptions required by filter based techniques. In addition, the electron bunch source size was measured by imaging a wire target, demonstrating few micron source size and stability. X-rays are generated when trapped electrons oscillate in the focusing field of the wake trailing the driver laser pulse. In addition to improving understanding of bunch emittance and wake structure, this provides a broadband, synchronized femtosecond source of keV x-rays. Electron bunch spectra and divergence were measured simultaneously and preliminary analysis shows correlation between x-ray andelectron spectra. Bremsstrahlung background was managed using shielding and magnetic diversion.

43 PARTICLE ACCELERATORS↗
DOE OSTI2012

Effects of electron-phonon coupling and electron diffusion on ripples growth on ultrafast-laser-irradiated metals

Metals exposed to ultrafast laser irradiation close to ablative regimes show often a submicron-scale (near 0.5 {mu}m) periodic organization of the surface as ripples. Using two classes of metallic materials (transition and noble), we have determined that the ripples amplitude is strongly correlated to the material transport properties, namely electron-phonon relaxation strength, electronic diffusion, and to the energy band characteristics of the electronic laser excitation. This particularly depends on the topology of the electronic structure, including d-band effects on electronic excitation. Comparing the effects of electron-phonon nonequilibrium lifetimes for the different metals under similar irradiation conditions, we indicate how the electron-phonon coupling strength affects the electronic thermal diffusion, the speed of phase transformation and impacts on the ripples contrast. The highest contrast is observed for ruthenium, where the electron-phonon coupling is the strongest, followed by tungsten, nickel, and copper, the latter with the least visible contrast. The dependence of surface patterns contrast with fluence is linked to the dependence of the relaxation characteristics with the electronic temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Water network-mediated, electron-induced proton transfer in [C{sub 5}H{sub 5}N ⋅ (H{sub 2}O){sub n}]{sup −} clusters

The role of proton-assisted charge accommodation in electron capture by a heterocyclic electron scavenger is investigated through theoretical analysis of the vibrational spectra of cold, gas phase [Py ⋅ (H{sub 2}O){sub n=3−5}]{sup −} clusters. These radical anions are formed when an excess electron is attached to water clusters containing a single pyridine (Py) molecule in a supersonic jet ion source. Under these conditions, the cluster ion distribution starts promptly at n = 3, and the photoelectron spectra, combined with vibrational predissociation spectra of the Ar-tagged anions, establish that for n > 3, these species are best described as hydrated hydroxide ions with the neutral pyridinium radical, PyH{sup (0)}, occupying one of the primary solvation sites of the OH{sup −}. The n = 3 cluster appears to be a special case where charge localization on Py and hydroxide is nearly isoenergetic, and the nature of this species is explored with ab initio molecular dynamics calculations of the trajectories that start from metastable arrangements of the anion based on a diffuse, essentially dipole-bound electron. These calculations indicate that the reaction proceeds via a relatively slow rearrangement of the water network to create a favorable hydration configuration around the water molecule that eventually donates a proton to the Py nitrogen atom to yield the product hydroxide ion. The correlation between the degree of excess charge localization and the evolving shape of the water network revealed by this approach thus provides a microscopic picture of the “solvent coordinate” at the heart of a prototypical proton-coupled electron transfer reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Effect of fast drifting electrons on electron temperature measurement with a triple Langmuir probe

Triple Langmuir Probe (TLP) is a widely used diagnostics for instantaneous measurement of electron temperature and density in low temperature laboratory plasmas as well as in edge region of fusion plasma devices. Presence of a moderately energetic flowing electron component, constituting only a small fraction of the bulk electrons, is also a generally observed scenario in plasma devices, where plasmas are produced by electron impact ionization of neutrals. A theoretical analysis of its effect on interpretation of the TLP data for bulk electron temperature measurement is presented here assuming electron velocity distribution is not deviating substantially from a Maxwellian. The study predicts conventional expression from standard TLP theory to give overestimated value of bulk electron temperature. Correction factor is significant and largely depends on population density, temperature, and energy of the fast component. Experimental verification of theoretical results is obtained in the magnetized plasma linear experimental device of Saha Institute of Nuclear Physics where plasma is produced by an electron cyclotron resonance method and known to have a fast flowing electron component.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗