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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Photoionization Modeling of Oxygen K Absorption in the Interstellar Medium: The Chandra Grating Spectra of XTE J1817-330

We present detailed analyses of oxygen K absorption in the interstellar medium (ISM) using four high-resolution Chandra spectra towards the X-ray low-mass binary XTE J1817-330. The 11-25 A broadband is described with a simple absorption model that takes into account the pileup effect and results in an estimate of the hydrogen column density. The oxygen K-edge region (21-25 A) is fitted with the physical warmabs model, which is based on a photoionization model grid generated with the XSTAR code with the most up-to-date atomic database. This approach allows a benchmark of the atomic data which involves wavelength shifts of both the K lines and photoionization cross sections in order to fit the observed spectra accurately. As a result we obtain: a column density of N(sub H) = 1.38 +/- 0.01 x 10(exp 21) cm(exp -2); ionization parameter of log xi = .2.70 +/- 0.023; oxygen abundance of A(sub O) = 0.689(exp +0.015./-0.010); and ionization fractions of O I/O = 0.911, O II/O = 0.077, and O III/O = 0.012 that are in good agreement with previous studies. Since the oxygen abundance in warmabs is given relative to the solar standard of Grevesse and Sauval (1998), a rescaling with the revision by Asplund et al. (2009) yields A(sub O) = 0.952(exp +0.020/-0.013, a value close to solar that reinforces the new standard. We identify several atomic absorption lines.K-alpha , K-beta, and K-gamma in O I and O II; and K-alpha in O III, O VI, and O VII--last two probably residing in the neighborhood of the source rather than in the ISM. This is the first firm detection of oxygen K resonances with principal quantum numbers n greater than 2 associated to ISM cold absorption.

Gatuzz, E.↗
NASA NTRS2019

Photoionization Calculations of the Radiation Force Due To Spectral Lines in AGNs

One of the main mechanisms that could drive mass outflows in active galactic nuclei (AGNs) is radiation pressure due to spectral lines. Although straightforward to understand, the actual magnitude of the radiation force is challenging to compute because the force depends on the physical conditions in the gas, as well as the strength, spectral energy distribution (SED), and geometry of the radiation field. We present results from our photoionization and radiation transfer calculations of the force multiplier, M(ξ, t), using the same radiation field to compute the gas photoionization and thermal balance. We assume low gas density (n = 104 per cu.cm) and column density (N ≤ 1017 per sq.cm), a Boltzmann distribution for the level populations, and the Sobolev approximation. Here, we describe results for two SEDs corresponding to an unobscured and obscured AGN in NGC 5548. Our main results are the following: (1) although M(ξ, t) starts to decrease with ξ for ξ gsim 1 as shown by others, this decrease in our calculations is relatively gradual and could be nonmonotonic as M(ξ, t) can increase by a factor of a few for ξ ≈ 10–1000; (2) at these same ξ for which the multiplier is higher than in previous calculations, the gas is thermally unstable by the isobaric criterion; (3) non-local thermodynamic equilibrium effects reduce M(t, ξ) by over two orders of magnitude for ξ gsim 100. The dynamical consequence of result (1) is that line driving can be important for ξ as high as 1000 when the LTE approximation holds, while result (2) provides a natural cloud formation mechanism that may account for the existence of narrow line regions. Result (3) suggests that line driving may not be important for ξ gsim 100 in tenuous plasma.

Dannen, Randall C.↗
DOE OSTI2017

Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds

Herein we report the observation of atmospheric pressure in-source hydrogen–deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D{sub 2}O

In this study, continuous in-source hydrogen/deuterium exchange (HDX) atmospheric pressure photoionization (APPI) mass spectrometry (MS) with continuous feeding of D{sub 2}O was developed and validated. D{sub 2}O was continuously fed using a capillary line placed on the center of a metal plate positioned between the UV lamp and nebulizer. The proposed system overcomes the limitations of previously reported APPI HDX-MS approaches where deuterated solvents were premixed with sample solutions before ionization. This is particularly important for APPI because solvent composition can greatly influence ionization efficiency as well as the solubility of analytes. The experimental parameters for APPI HDX-MS with continuous feeding of D{sub 2}O were optimized, and the optimized conditions were applied for the analysis of nitrogen-, oxygen-, and sulfur-containing compounds. The developed method was also applied for the analysis of the polar fraction of a petroleum sample. Thus, the data presented in this study clearly show that the proposed HDX approach can serve as an effective analytical tool for the structural analysis of complex mixtures. .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Photoionization of C 60 at high energies

Calculations of the photoionization cross section of C60 including all valence and core subshells have been carried out for photon energies up to 1 keV using density functional theory (DFT) and time-dependent DFT (TDDFT) within the framework of a fully molecular model. The high-energy valence subshell cross sections behave rather differently than the results from model potentials where the cross section falls far too rapidly with energy. This unphysical behavior of the model calculations is traced to smearing out of the carbon nuclei in the model potentials which makes it difficult for momentum to be conserved at the higher energies. Comparison with 60 times carbon atomic cross section sheds light on similarities and differences. The high energy behavior of individual valence cross sections reflects the amount of C 2s/2p mixing in the molecular orbitals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Photoionization energetics and dissociation pathways of hydroperoxyethyl formate produced in the reaction of CH 3 CHOO + formic acid

The bimolecular reaction of Criegee intermediates, zwitterionic carbonyl oxide species produced in alkene ozonolysis, with organic acids leads to formation of functional hydroperoxides implicated in the generation of atmospheric aerosols. This theoretical study using high-level explicitly correlated coupled-cluster theory examines the low energy conformers of hydroperoxyethyl formate [HOOCH(CH 3 )OCHO, HPEF] formed in the bimolecular reaction of CH 3 CHOO, a simple alkyl-substituted Criegee intermediate, with formic acid, and the detection of HPEF via photoionization. Here, the vertical and adiabatic ionization energies of HPEF are computed, along with the pathways for dissociative ionization that produce HO 2 or OCHO fragments with daughter ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Development of spatially and temporally resolved electron density measurements for the assessment of radiation hydrodynamics simulations of laboratory X-ray photoionized plasmas

The photoionized plasma gas cell experiment is an established platform we use to make at-parameter (ξ > > 1 ergs cm s –1 ) measurements of plasma properties with application to high-energy astrophysical systems. We model the experiments with 1D radiation hydrodynamics simulations using the HELIOS-CR code to inform our understanding and assist in the interpretation of results. The simulations predict that the bulk of the plasma is in a quasi-uniform and hydrodynamically unperturbed state throughout the duration of the experiment. To evaluate this prediction, we introduced a photonic Doppler velocimetry (PDV) diagnostic to measure spatially and temporally resolved plasma electron density. The initial measurements were successful but had limitations that made model-data comparisons challenging. To address this, we re-designed the gas cell PDV diagnostic and doubled the number of measurement locations to sample across two thirds of the depth of the cell. We also present a comparison of the results from the upgraded PDV diagnostic to the HELIOS-CR simulations for the first time. As a result, the experimental data confirms the prediction of an unperturbed region in the bulk of the plasma but reveals discrepancies in the time evolution and spatial distribution of the simulated electron density.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

The product formation from R + O 2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO 2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O 2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O 2 -addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.

2,2,5,5-tetramethyl-tetrahydrofuran↗
DOE OSTI2012

Kinetic theory of magnetized dusty plasmas with dust particles charged by collisional processes and by photoionization

In this work, we detail the derivation of a plasma kinetic theory leading to the components of the dielectric tensor for a magnetized dusty plasma with variable charge on the dust particles, considering that the dust component of the plasma contains spherical dust particles with different sizes, which are charged both by inelastic collisions of electrons and ions and by photoionization.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2012

Rovibrationally selected ion-molecule collision study using the molecular beam vacuum ultraviolet laser pulsed field ionization-photoion method: Charge transfer reaction of N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2; N{sup +}= 0-9) + Ar

We have developed an ion-molecule reaction apparatus for state-selected absolute total cross section measurements by implementing a high-resolution molecular beam vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) ion source to a double-quadrupole double-octopole ion-guide mass spectrometer. Using the total cross section measurement of the state-selected N{sub 2}{sup +}(v{sup +}, N{sup +}) + Ar charge transfer (CT) reaction as an example, we describe in detail the design of the VUV laser PFI-PI ion source used, which has made possible the preparation of reactant N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}, v{sup +}= 0-2, N{sup +}= 0-9) PFI-PIs with high quantum state purity, high intensity, and high kinetic energy resolution. The PFI-PIs and prompt ions produced in the ion source are shown to have different kinetic energies, allowing the clean rejection of prompt ions from the PFI-PI beam by applying a retarding potential barrier upstream of the PFI-PI source. By optimizing the width and amplitude of the pulsed electric fields employed to the VUV-PFI-PI source, we show that the reactant N{sub 2}{sup +} PFI-PI beam can be formed with a laboratory kinetic energy resolution of {Delta}E{sub lab}={+-} 50 meV. As a result, the total cross section measurement can be conducted at center-of-mass kinetic energies (E{sub cm}'s) down to thermal energies. Absolute total rovibrationally selected cross sections {sigma}(v{sup +}= 0-2, N{sup +}= 0-9) for the N{sub 2}{sup +}(X {sup 2}{Sigma}{sub g}{sup +}; v{sup +}= 0-2, N{sup +}= 0-9) + Ar CT reaction have been measured in the E{sub cm} range of 0.04-10.0 eV, revealing strong vibrational enhancements and E{sub cm}-dependencies of {sigma}(v{sup +}= 0-2, N{sup +}= 0-9). The thermochemical threshold at E{sub cm}= 0.179 eV for the formation of Ar{sup +} from N{sub 2}{sup +}(X; v{sup +}= 0, N{sup +}) + Ar was observed by the measured {sigma}(v{sup +}= 0), confirming the narrow {Delta}E{sub cm} spread achieved in the present study. The {sigma}(v{sup +}= 0-2; N{sup +}) values obtained here are compared with previous experimental and theoretical results. The theoretical predictions calculated based on the Landau-Zener-Stueckelberg formulism are found to be in fair agreement with the present measured {sigma}(v{sup +}= 1 or 2; N{sup +}). Taking into account of the experimental uncertainties, the measured {sigma}(v{sup +}= 1 or 2, N{sup +}) for N{sup +}= 0-9 at E{sub cm}= 0.04-10.0 eV are found to be independent of N{sup +}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Photoionization of optically trapped ultracold atoms with a high-power light-emitting diode

Photoionization of laser-cooled atoms using short pulses of a high-power light-emitting diode (LED) is demonstrated. Light pulses as short as 30 ns have been realized with the simple LED driver circuit. We measure the ionization cross section of {sup 85}Rb atoms in the first excited state, and show how this technique can be used for calibrating efficiencies of ion detector assemblies.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2013

Role of excited state photoionization in the 852.1 nm Cs laser pumped by Cs-Ar photoassociation

Photoionization of Cs (6p {sup 2}P{sub 3/2}) atoms during the operation of a Cs D{sub 2} line (852.1 nm: 6p {sup 2}P{sub 3/2}{yields}6s {sup 2}S{sub 1/2}) laser, pumped by free{yields}free transitions of thermal Cs-Ar ground state pairs, has been investigated experimentally and computationally. Photoexcitation of Cs vapor/Ar mixtures through the blue satellite of the D{sub 2} transition (peaking at 836.7 nm) selectively populates the {sup 2}P{sub 3/2} upper laser level by the dissociation of the CsAr excited complex. Comparison of laser output energy data, for instantaneous pump powers up to 3 MW, with the predictions of a numerical model sets an upper bound of 8 Multiplication-Sign 10{sup -26} cm{sup 4} W{sup -1} on the Cs (6p {sup 2}P{sub 3/2}) two photon ionization cross-section at 836.7 nm which corresponds to a single photon cross-section of 2.4 Multiplication-Sign 10{sup -19} cm{sup 2} for a peak pump intensity of 3 MW cm{sup -2}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2013

Photoionization cross section by Stieltjes imaging applied to coupled cluster Lanczos pseudo-spectra

A recently implemented asymmetric Lanczos algorithm for computing (complex) linear response functions within the coupled cluster singles (CCS), coupled cluster singles and iterative approximate doubles (CC2), and coupled cluster singles and doubles (CCSD) is coupled to a Stieltjes imaging technique in order to describe the photoionization cross section of atoms and molecules, in the spirit of a similar procedure recently proposed by Averbukh and co-workers within the Algebraic Diagrammatic Construction approach. Pilot results are reported for the atoms He, Ne, and Ar and for the molecules H{sub 2}, H{sub 2}O, NH{sub 3}, HF, CO, and CO{sub 2}.

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

Effect of strongly coupled plasma on photoionization cross section

The effect of strongly coupled plasma on the ground state photoionization cross section is studied. In the non relativistic dipole approximation, cross section is evaluated from bound-free transition matrix element. The bound and free state wave functions are obtained by solving the radial Schrodinger equation with appropriate plasma potential. We have used ion sphere potential (ISP) to incorporate the plasma effects in atomic structure calculation. This potential includes the effect of static plasma screening on nuclear charge as well as the effect of confinement due to the neighbouring ions. With ISP, the radial equation is solved using Shooting method approach for hydrogen like ions (Li{sup +2}, C{sup +5}, Al{sup +12}) and lithium like ions (C{sup +3}, O{sup +5}). The effect of strong screening and confinement is manifested as confinement resonances near the ionization threshold for both kinds of ions. The confinement resonances are very much dependent on the edge of the confining potential and die out as the plasma density is increased. Plasma effect also results in appearance of Cooper minimum in lithium like ions, which was not present in case of free lithium like ions. With increasing density the position of Cooper minimum shifts towards higher photoelectron energy. The same behaviour is also true for weakly coupled plasma where plasma effect is modelled by Debye-Huckel potential.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Vacuum ultraviolet photoionization of carbohydrates and nucleotides

Carbohydrates (2-deoxyribose, ribose, and xylose) and nucleotides (adenosine-, cytidine-, guanosine-, and uridine-5{sup ′}-monophosphate) are generated in the gas phase, and ionized with vacuum ultraviolet photons (VUV, 118.2 nm). The observed time of flight mass spectra of the carbohydrate fragmentation are similar to those observed [J.-W. Shin, F. Dong, M. Grisham, J. J. Rocca, and E. R. Bernstein, Chem. Phys. Lett. 506, 161 (2011)] for 46.9 nm photon ionization, but with more intensity in higher mass fragment ions. The tendency of carbohydrate ions to fragment extensively following ionization seemingly suggests that nucleic acids might undergo radiation damage as a result of carbohydrate, rather than nucleobase fragmentation. VUV photoionization of nucleotides (monophosphate-carbohydrate-nucleobase), however, shows that the carbohydrate-nucleobase bond is the primary fragmentation site for these species. Density functional theory (DFT) calculations indicate that the removed carbohydrate electrons by the 118.2 nm photons are associated with endocyclic C–C and C–O ring centered orbitals: loss of electron density in the ring bonds of the nascent ion can thus account for the observed fragmentation patterns following carbohydrate ionization. DFT calculations also indicate that electrons removed from nucleotides under these same conditions are associated with orbitals involved with the nucleobase-saccharide linkage electron density. The calculations give a general mechanism and explanation of the experimental results.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Communication: State-to-state photoionization and photoelectron study of vanadium methylidyne radical (VCH)

By employing the infrared (IR)-ultraviolet (UV) laser excitation scheme, we have obtained rotationally selected and resolved pulsed field ionization-photoelectron (PFI-PE) spectra for vanadium methylidyne cation (VCH{sup +}). This study supports that the ground state electronic configuration for VCH{sup +} is …7σ{sup 2}8σ{sup 2}3π{sup 4}9σ{sup 1} (X{sup ~2}Σ{sup +}), and is different from that of …7σ{sup 2}8σ{sup 2}3π{sup 4}1δ{sup 1} (X{sup ~2}Δ) for the isoelectronic TiO{sup +} and VN{sup +} ions. This observation suggests that the addition of an H atom to vanadium carbide (VC) to form VCH has the effect of stabilizing the 9σ orbital relative to the 1δ orbital. The analysis of the state-to-state IR-UV-PFI-PE spectra has provided precise values for the ionization energy of VCH, IE(VCH) = 54 641.9 ± 0.8 cm{sup −1} (6.7747 ± 0.0001 eV), the rotational constant B{sup +} = 0.462 ± 0.002 cm{sup −1}, and the v{sub 2}{sup +} bending (626 ± 1 cm{sup −1}) and v{sub 3}{sup +} V–CH stretching (852 ± 1 cm{sup −1}) vibrational frequencies for VCH{sup +}(X{sup ~2}Σ{sup +}). The IE(VCH) determined here, along with the known IE(V) and IE(VC), allows a direct measure of the change in dissociation energy for the V–CH as well as the VC–H bond upon removal of the 1δ electron of VCH(X{sup ~3}Δ{sub 1}). The formation of VCH{sup +}(X{sup ~2}Σ{sup +}) from VCH(X{sup ~3}Δ{sub 1}) by photoionization is shown to strengthen the VC–H bond by 0.3559 eV, while the strength of the V–CH bond remains nearly unchanged. This measured change of bond dissociation energies reveals that the highest occupied 1δ orbital is nonbonding for the V–CH bond; but has anti-bonding or destabilizing character for the VC–H bond of VCH(X{sup ~3}Δ{sub 1})

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

Photoionization of cold gas phase coronene and its clusters: Autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation

Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

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

B-spline algebraic diagrammatic construction: Application to photoionization cross-sections and high-order harmonic generation

We present the first implementation of the ab initio many-body Green's function method, algebraic diagrammatic construction (ADC), in the B-spline single-electron basis. B-spline versions of the first order [ADC(1)] and second order [ADC(2)] schemes for the polarization propagator are developed and applied to the ab initio calculation of static (photoionization cross-sections) and dynamic (high-order harmonic generation spectra) quantities. We show that the cross-section features that pose a challenge for the Gaussian basis calculations, such as Cooper minima and high-energy tails, are found to be reproduced by the B-spline ADC in a very good agreement with the experiment. We also present the first dynamic B-spline ADC results, showing that the effect of the Cooper minimum on the high-order harmonic generation spectrum of Ar is correctly predicted by the time-dependent ADC calculation in the B-spline basis. The present development paves the way for the application of the B-spline ADC to both energy- and time-resolved theoretical studies of many-electron phenomena in atoms, molecules, and clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗