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At least 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Three-dimensional, two-species magnetohydrodynamic studies of the early time behaviors of the Combined Release and Radiation Effects Satellite G2 barium release

We present a three-dimensional, two-species (Ba{sup +} and H{sup +}) MHD model to study the early time behaviors of a barium release at about 1 R{sub E} like Combined Release and Radiation Effects Satellite G2, with emphasis placed on the three-dimensional evolution of the barium cloud and its effects on the ambient plasma environment. We find that the perturbations caused by the cloud are the combined results of the initial injection, the radial expansion, and the diamagnetic effect and propagate as fast MHD waves in the magnetosphere. In return, the transverse expansion and the cross-B motion of barium ions are constrained by the magnetic force, which lead to a field-aligned striation of ions and the decoupling of these ions from the neutrals. Our simulation shows the formation and collapse of the diamagnetic cavity in the barium cloud. The estimated time scale for the cavity evolution might be much shorter if photoionization time scale and field aligned expansion of barium ions are considered. In addition, our two species MHD simulation also finds the snowplow effect resulting from the momentum coupling between barium ions and background H{sup +}, which creates density hole and bumps in the background H{sup +} when barium ions expanding along the magnetic field lines.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Photofragmentation spectra of halogenated methanes in the VUV photon energy range

In this paper an investigation of the photofragmentation of dihalomethanes CH{sub 2}X{sub 2} (X = F, Cl, Br, I) and chlorinated methanes (CH{sub n}Cl{sub 4−n} with n = 0–3) with VUV helium, neon, and argon discharge lamps is reported and the role played by the different halogen atoms is discussed. Halogenated methanes are a class of molecules used in several fields of chemistry and the study of their physical and chemical proprieties is of fundamental interest. In particular their photodissociation and photoionization are of great importance since the decomposition of these compounds in the atmosphere strongly affects the environment. The results of the present work show that the halogen-loss is the predominant fragmentation channel for these molecules in the VUV photon energy range and confirm their role as reservoir of chlorine, bromine, and iodine atoms in the atmosphere. Moreover, the results highlight the peculiar feature of CH{sub 2}F{sub 2} as a source of both fluorine and hydrogen atoms and the characteristic formation of I{sub 2}{sup +} and CH{sub 2}{sup +} ions from the photofragmentation of the CH{sub 2}I{sub 2} molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Rotationally resolved state-to-state photoelectron study of niobium carbide radical

By employing the two-color visible (VIS)-ultraviolet (UV) laser photoexcitation scheme and the pulsed field ionization-photoelectron (PFI-PE) detection, we have obtained rovibronically selected and resolved photoelectron spectra for niobium carbide cation (NbC{sup +}). The fully rotationally resolved state-to-state VIS-UV-PFI-PE spectra thus obtained allow the unambiguous assignments of rotational photoionization transitions, indicating that the electronic configuration and term symmetry of NbC{sup +}(X{sup ~}) ground state are …10σ{sup 2} 5π{sup 4} 11σ{sup 2} (X{sup ~1}Σ{sup +}). Furthermore, the rotational analysis of these spectra yields the ionization energy of NbC [IE(NbC)] to be 56 369.2 ± 0.8 cm{sup −1} (6.9889 ± 0.0001 eV) and the rotation constant B{sub 0}{sup +} = 0.5681 ± 0.0007 cm{sup −1}. The latter value allows the determination of the bond distance r{sub 0}{sup +} = 1.671 ± 0.001 Å for NbC{sup +}(X{sup ~1}Σ{sup +}). Based on conservation of energy, the IE(NbC) determined in the present study along with the known IE(Nb) gives the difference of 0 K bond dissociation energies (D{sub 0}’s) for NbC{sup +} and NbC, D{sub 0}(NbC{sup +}) − D{sub 0}(NbC) = −1855.4 ± 0.9 cm{sup −1} (−0.2300 ± 0.0001 eV). The energetic values and the B{sub 0}{sup +} constant determined in this work are valuable for benchmarking state-of-the-art ab initio quantum calculations of 4d transition metal-containing molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

The cyclopropene radical cation: Rovibrational level structure at low energies from high-resolution photoelectron spectra

The cyclopropene radical cation (c-C{sub 3}H{sub 4}{sup +}) is an important but poorly characterized three-membered-ring hydrocarbon. We report on a measurement of the high-resolution photoelectron and photoionization spectra of cyclopropene and several deuterated isotopomers, from which we have determined the rovibrational energy level structure of the X{sup ~+} {sup 2}B{sub 2} ground electronic state of c-C{sub 3}H{sub 4}{sup +} at low energies for the first time. The synthesis of the partially deuterated isotopomers always resulted in mixtures of several isotopomers, differing in their number of D atoms and in the location of these atoms, so that the photoelectron spectra of deuterated samples are superpositions of the spectra of several isotopomers. The rotationally resolved spectra indicate a C{sub 2v}-symmetric R{sub 0} structure for the ground electronic state of c-C{sub 3}H{sub 4}{sup +}. Two vibrational modes of c-C{sub 3}H{sub 4}{sup +} are found to have vibrational wave numbers below 300 cm{sup −1}, which is surprising for such a small cyclic hydrocarbon. The analysis of the isotopic shifts of the vibrational levels enabled the assignment of the lowest-frequency mode (fundamental wave number of ≈110 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to the CH{sub 2} torsional mode (ν{sub 8}{sup +}, A{sub 2} symmetry) and of the second-lowest-frequency mode (≈210 cm{sup −1} in c-C{sub 3}H{sub 4}{sup +}) to a mode combining a CH out-of-plane with a CH{sub 2} rocking motion (ν{sub 15}{sup +}, B{sub 2} symmetry). The potential energy along the CH{sub 2} torsional coordinate is flat near the equilibrium structure and leads to a pronounced anharmonicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Probing the structural dependency of photoinduced properties of colloidal quantum dots using metal-oxide photo-active substrates

We used photoactive substrates consisting of about 1 nm coating of a metal oxide on glass substrates to investigate the impact of the structures of colloidal quantum dots on their photophysical and photochemical properties. We showed during irradiation these substrates can interact uniquely with such quantum dots, inducing distinct forms of photo-induced processes when they have different cores, shells, or ligands. In particular, our results showed that for certain types of core-shell quantum dot structures an ultrathin layer of a metal oxide can reduce suppression of quantum efficiency of the quantum dots happening when they undergo extensive photo-oxidation. This suggests the possibility of shrinking the sizes of quantum dots without significant enhancement of their non-radiative decay rates. We show that such quantum dots are not influenced significantly by Coulomb blockade or photoionization, while those without a shell can undergo a large amount of photo-induced fluorescence enhancement via such blockade when they are in touch with the metal oxide.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Dynamics of the reaction of C{sub 3}(a{sup 3}Π{sub u}) radicals with C{sub 2}H{sub 2}: A new source for the formation of C{sub 5}H

The reaction C{sub 3}(a{sup 3}Π{sub u}) + C{sub 2}H{sub 2} → C{sub 5}H + H was investigated at collision energy 10.9 kcal mol{sup −1} that is less than the enthalpy of ground-state reaction C{sub 3}(X{sup 1}Σ{sub g}{sup +}) + C{sub 2}H{sub 2} → C{sub 5}H + H. C{sub 3}(a{sup 3}Π{sub u}) radicals were synthesized from 1% C{sub 4}F{sub 6}/He by pulsed high-voltage discharge. The title reaction was conducted in a crossed molecular-beam apparatus equipped with a quadrupole-mass filter. Product C{sub 5}H was interrogated with time-of-flight spectroscopy and synchrotron vacuum-ultraviolet ionization. Reactant C{sub 3}(a{sup 3}Π{sub u}) and product C{sub 5}H were identified using photoionization spectroscopy. The ionization thresholds of C{sub 3}(X{sup 1}Σ{sub g}{sup +}) and C{sub 3}(a{sup 3}Π{sub u}) are determined as 11.6 ± 0.2 eV and 10.0 ± 0.2 eV, respectively. The C{sub 5}H product is identified as linear pentynylidyne that has an ionization energy 8.4 ± 0.2 eV. The title reaction releases translational energy 10.6 kcal mol{sup −1} in average and has an isotropic product angular distribution. The quantum-chemical calculation indicates that the C{sub 3}(a{sup 3}Π{sub u}) radical attacks one of the carbon atoms of C{sub 2}H{sub 2} and subsequently a hydrogen atom is ejected to form C{sub 5}H + H, in good agreement with the experimental observation. As far as we are aware, the C{sub 3}(a{sup 3}Π{sub u}) + C{sub 2}H{sub 2} reaction is investigated for the first time. This work gives an implication for the formation of C{sub 5}H from the C{sub 3}(a{sup 3}Π{sub u}) + C{sub 2}H{sub 2} reaction occurring in a combustion or discharge process of C{sub 2}H{sub 2}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

System for time-discretized vacuum ultraviolet spectroscopy of spark breakdown in air

A system for time-discretized spectroscopic measurements of the vacuum ultraviolet (VUV) emission from spark discharges in the 60-160 nm range has been developed for the study of early plasma-forming phenomena. The system induces a spark discharge in an environment close to atmospheric conditions created using a high speed puff value, but is otherwise kept at high vacuum to allow for the propagation of VUV light. Using a vertical slit placed 1.5 mm from the discharge the emission from a small cross section of the discharge is allowed to pass into the selection chamber consisting of a spherical grating, with 1200 grooves/mm, and an exit slit set to 100 μm. Following the exit slit is a photomultiplier tube with a sodium salicylate scintillator that is used for the time discretized measurement of the VUV signal with a temporal resolution limit of 10 ns. Results from discharges studied in dry air, Nitrogen, SF{sub 6}, and Argon indicate the emission of light with wavelengths shorter than 120 nm where the photon energy begins to approach the regime of direct photoionization.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2014

A coupled-cluster study of photodetachment cross sections of closed-shell anions

We investigate the performance of Stieltjes Imaging applied to Lanczos pseudo-spectra generated at the coupled cluster singles and doubles, coupled cluster singles and approximate iterative doubles and coupled cluster singles levels of theory in modeling the photodetachment cross sections of the closed shell anions H{sup −}, Li{sup −}, Na{sup −}, F{sup −}, Cl{sup −}, and OH{sup −}. The accurate description of double excitations is found to play a much more important role than in the case of photoionization of neutral species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure

Ionization energies and cationic structures of pyridine were intensively investigated utilizing one-photon mass-analyzed threshold ionization (MATI) spectroscopy with vacuum ultraviolet radiation generated by four-wave difference frequency mixing in Kr. The present one-photon high-resolution MATI spectrum of pyridine demonstrated a much finer and richer vibrational structure than that of the previously reported two-photon MATI spectrum. From the MATI spectrum and photoionization efficiency curve, the accurate ionization energy of the ionic ground state of pyridine was confidently determined to be 73 570 ± 6 cm{sup −1} (9.1215 ± 0.0007 eV). The observed spectrum was almost completely assigned by utilizing Franck-Condon factors and vibrational frequencies calculated through adjustments of the geometrical parameters of cationic pyridine at the B3LYP/cc-pVTZ level. A unique feature unveiled through rigorous analysis was the prominent progression of the 10 vibrational mode, which corresponds to in-plane ring bending, and the combination of other totally symmetric fundamentals with the ring bending overtones, which contribute to the geometrical change upon ionization. Notably, the remaining peaks originate from the upper electronic state ({sup 2}A{sub 2}), as predicted by high-resolution photoelectron spectroscopy studies and symmetry-adapted cluster configuration interaction calculations. Based on the quantitatively good agreement between the experimental and calculated results, it was concluded that upon ionization the pyridine cation in the ground electronic state should have a planar structure of C{sub 2v} symmetry through the C-N axis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Dynamics of the reaction of C{sub 2} with C{sub 6}H{sub 2}: An implication for the formation of interstellar C{sub 8}H

The reaction C{sub 2} + C{sub 6}H{sub 2} → C{sub 8}H + H was investigated for the first time. Reactant C{sub 2} (C{sub 6}H{sub 2}) was synthesized from 1% C{sub 3}F{sub 6}/He (5% C{sub 2}H{sub 2}/He) by pulsed high-voltage discharge. We measured the translational-energy distribution, the angular distribution, and the photoionization spectrum of product C{sub 8}H in a crossed molecular-beam apparatus using synchrotron vacuum-ultraviolet ionization. This reaction released average translational energy of 8.5 kcal mol{sup −1} corresponding to a fraction of 0.37 in translation. C{sub 8}H was identified as octatetranyl based on the maximal translational-energy release 23 ± 2 kcal mol{sup −1} and the ionization threshold 8.9 ± 0.2 eV. Kinematic constraints can qualitatively account for the nearly isotropic angular distribution. The quantum-chemical calculations indicate that the exothermic reactions C{sub 2} (X {sup 1}Σ{sub g}{sup +}/a {sup 3}Π{sub u}) + HC{sub 6}H → C{sub 8}H + H can proceed without entrance and exit barriers, implying the importance in the cold interstellar medium. This work verifies that interstellar C{sub 8}H can be formed through the C{sub 2} + C{sub 6}H{sub 2} reaction.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Certifying the quantumness of a generalized coherent control scenario

We consider the role of quantum mechanics in a specific coherent control scenario, designing a “coherent control interferometer” as the essential tool that links coherent control to quantum fundamentals. Building upon this allows us to rigorously display the genuinely quantum nature of a generalized weak-field coherent control scenario (utilizing 1 vs. 2 photon excitation) via a Bell-CHSH test. Specifically, we propose an implementation of “quantum delayed-choice” in a bichromatic alkali atom photoionization experiment. The experimenter can choose between two complementary situations, which are characterized by a random photoelectron spin polarization with particle-like behavior on the one hand, and by spin controllability and wave-like nature on the other. Because these two choices are conditioned coherently on states of the driving fields, it becomes physically unknowable, prior to measurement, whether there is control over the spin or not.

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

Single photon simultaneous K-shell ionization and K-shell excitation. I. Theoretical model applied to the interpretation of experimental results on H{sub 2}O

We present in detail a theoretical model that provides absolute cross sections for simultaneous core-ionization core-excitation (K{sup −2}V ) and compare its predictions with experimental results obtained on the water molecule after photoionization by synchrotron radiation. Two resonances of different symmetries are assigned in the main K{sup −2}V peak and comparable contributions from monopolar (direct shake-up) and dipolar (conjugate shake-up) core-valence excitations are identified. The main peak is observed with a much greater width than the total experimental resolution. This broadening is the signature of nuclear dynamics.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Near edge X-ray absorption mass spectrometry on coronene

We have investigated the photoionization and photodissociation of free coronene cations C{sub 24}H{sub 12}{sup +} upon soft X-ray photoabsorption in the carbon K-edge region by means of a time-of-flight mass spectrometry approach. Core excitation into an unoccupied molecular orbital (below threshold) and core ionization into the continuum both leave a C 1s vacancy, that is subsequently filled in an Auger-type process. The resulting coronene dications and trications are internally excited and cool down predominantly by means of hydrogen emission. Density functional theory was employed to determine the dissociation energies for subsequent neutral hydrogen loss. A statistical cascade model incorporating these dissociation energies agrees well with the experimentally observed dehydrogenation. For double ionization, i.e., formation of intermediate C{sub 24}H{sub 12}{sup 3+⋆}trications, the experimental data hint at loss of H{sup +} ions. This asymmetric fission channel is associated with hot intermediates, whereas colder intermediates predominantly decay via neutral H loss.

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

Predissociation dynamics of lithium iodide

The predissociation dynamics of lithium iodide (LiI) in the first excited A-state is investigated for molecules in the gas phase and embedded in helium nanodroplets, using femtosecond pump-probe photoionization spectroscopy. In the gas phase, the transient Li{sup +} and LiI{sup +} ion signals feature damped oscillations due to the excitation and decay of a vibrational wave packet. Based on high-level ab initio calculations of the electronic structure of LiI and simulations of the wave packet dynamics, the exponential signal decay is found to result from predissociation predominantly at the lowest avoided X-A potential curve crossing, for which we infer a coupling constant V{sub XA} = 650(20) cm{sup −1}. The lack of a pump-probe delay dependence for the case of LiI embedded in helium nanodroplets indicates fast droplet-induced relaxation of the vibrational excitation.

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

Infrared spectra of small molecular ions trapped in solid neon

The infrared spectrum of a molecular ion provides a unique signature for that species, gives information on its structure, and is amenable to remote sensing. It also serves as a comparison standard for refining ab initio calculations. Experiments in this laboratory trap molecular ions in dilute solid solution in neon at 4.2 K in sufficient concentration for observation of their infrared spectra between 450 and 4000 cm{sup !1}. Discharge-excited neon atoms produce cations by photoionization and/or Penning ionization of the parent molecule. The resulting electrons are captured by other molecules, yielding anions which provide for overall charge neutrality of the deposit. Recent observations of ions produced from C{sub 2}H{sub 4} and BF{sub 3} will be discussed. Because of their relatively large possibility of having low-lying excited electronic states, small, symmetric molecular cations are especially vulnerable to breakdown of the Born-Oppenheimer approximation. Some phenomena which can result from this breakdown will be discussed. Ion-molecule reaction rates are sufficiently high that in some systems absorptions of dimer cations and anions are also observed. When H{sub 2} is introduced into the system, the initially-formed ion may react with it. Among the species resulting from such ion-molecule reactions that have recently been studied are O{sub 4}{sup +}, NH{sub 4}{sup +}, HOCO{sup +}, and HCO{sub 2}{sup !}.

74 ATOMIC AND MOLECULAR PHYSICS↗