TL;DR: In this article, the authors present a comprehensive set of FDCSs for single ionization of atoms by ion-impact, the most basic atomic fragmentation reaction, brought new insight, a couple of surprises and unexpected challenges to theory at keV to GeV collision energies.
Abstract: Recoil-ion and electron momentum spectroscopy is a rapidly developing technique that allows one to measure the vector momenta of several ions and electrons resulting from atomic or molecular fragmentation. In a unique combination, large solid angles close to 4π and superior momentum resolutions around a few per cent of an atomic unit (a.u.) are typically reached in state-of-the art machines, so-called reaction-microscopes. Evolving from recoil-ion and cold target recoil-ion momentum spectroscopy (COLTRIMS), reaction-microscopes—the `bubble chambers of atomic physics'—mark the decisive step forward to investigate many-particle quantum-dynamics occurring when atomic and molecular systems or even surfaces and solids are exposed to time-dependent external electromagnetic fields. This paper concentrates on just these latest technical developments and on at least four new classes of fragmentation experiments that have emerged within about the last five years. First, multi-dimensional images in momentum space brought unprecedented information on the dynamics of single-photon induced fragmentation of fixed-in-space molecules and on their structure. Second, a break-through in the investigation of high-intensity short-pulse laser induced fragmentation of atoms and molecules has been achieved by using reaction-microscopes. Third, for electron and ion-impact, the investigation of two-electron reactions has matured to a state such that the first fully differential cross sections (FDCSs) are reported. Fourth, comprehensive sets of FDCSs for single ionization of atoms by ion-impact, the most basic atomic fragmentation reaction, brought new insight, a couple of surprises and unexpected challenges to theory at keV to GeV collision energies. In addition, a brief summary on the kinematics is provided at the beginning. Finally, the rich future potential of the method is briefly envisaged.
TL;DR: It is determined that N2 molecules are four times more likely to ionize when aligned parallel to the field than when aligned perpendicular to it, which indicates the dependence of strong field ionization of N2 on molecular orientation.
Abstract: We demonstrate a method to measure strong field laser ionization of aligned molecules. The method employs a macroscopic field-free dynamic alignment, which occurs during revivals of rotational wave packets produced by a femtosecond laser pulse. We investigate the dependence of strong field ionization of ${\mathrm{N}}_{\mathrm{2}}$ on molecular orientation. We determine that ${\mathrm{N}}_{\mathrm{2}}$ molecules are four times more likely to ionize when aligned parallel to the field than when aligned perpendicular to it.
TL;DR: In this article, the effect of ionization on the physical properties of aerosols and clouds has been studied in its own right except in thunderstorms, and the authors conclude that a mechanism linking cosmic ray ionization and cloud properties cannot be excluded and that there are established electrical effects on aerosol and cloud microphysics.
Abstract: [1] Natural terrestrial radioactivity and cosmic ray ionization lead to the formation of air ions and charged aerosol particles even away from regions of active charge separation, such as in thunderstorms. The natural electrified state of the atmosphere has been studied for over a century; however, the effect of ionization on the physical properties of aerosols and clouds has rarely been studied in its own right except in thunderstorms. Here we review the status of our understanding of atmospheric charged particles and their influence on aerosol and cloud microphysical processes. We also review mechanisms that have been recently proposed to connect variations in the atmospheric ionization rate with variations in global cloudiness and weather systems. We conclude that a mechanism linking cosmic ray ionization and cloud properties cannot be excluded and that there are established electrical effects on aerosol and cloud microphysics. Necessary further work includes measurements of cloud, droplet, and aerosol charging and ion-aerosol conversion, together with modeling of the electrical aspects of nonthunderstorm cloud microphysics.
TL;DR: In this paper, a direct experimental measurement of the H3+ destruction rate under nearly interstellar conditions is reported, where the electron fraction is already known and the cosmic-ray ionization rate along this line of sight is 40 times faster than previously assumed.
Abstract: The H3+ molecular ion plays a fundamental role in interstellar chemistry, as it initiates a network of chemical reactions that produce many molecules1,2. In dense interstellar clouds, the H3+ abundance is understood using a simple chemical model, from which observations of H3+ yield valuable estimates of cloud path length, density and temperature3,4. But observations of diffuse clouds have suggested that H3+ is considerably more abundant than expected from the chemical models5,6,7. Models of diffuse clouds have, however, been hampered by the uncertain values of three key parameters: the rate of H3+ destruction by electrons (e-), the electron fraction, and the cosmic-ray ionization rate. Here we report a direct experimental measurement of the H3+ destruction rate under nearly interstellar conditions. We also report the observation of H3+ in a diffuse cloud (towards ζ Persei) where the electron fraction is already known. From these, we find that the cosmic-ray ionization rate along this line of sight is 40 times faster than previously assumed. If such a high cosmic-ray flux is ubiquitous in diffuse clouds, the discrepancy between chemical models and the previous observations5,6,7 of H3+ can be resolved.
TL;DR: It has been found that carbon nanotubes can transfer energy to the analyte under laser irradiation, which makes analytes well desorbed/ionized, and the interference of intrinsic matrix ions can be eliminated.
Abstract: Analysis of low molecular weight compounds with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been developed by using carbon nanotubes obtained from coal by arc discharge as the matrix. The carbon nanotube matrix functions as substrate to trap analytes of peptides, organic compounds, and beta-cyclodextrin deposited on its surface. It has been found that carbon nanotubes can transfer energy to the analyte under laser irradiation, which makes analytes well desorbed/ionized, and the interference of intrinsic matrix ions can be eliminated. At the same time, the fragmentation of the analyte can be avoided. A good sensitivity and excellent reproducibility of the spectrum signals are achieved. It is believed that this work not only will open a new field for applications of carbon nanotubes, but also will offer a new technique for high-speed analysis of low molecular weight compounds in areas such as metabolism research and characterization of natural products.
TL;DR: In this paper, a three-dimensional (3D) ion velocity imaging method was developed to measure the product velocity distributions in crossed molecular beam experiments, while maintaining conventional two-dimensional velocity mapping, the third velocity component was mapped linearly to the ion time of flight.
Abstract: A three-dimensional (3D) ion velocity imaging method was developed to measure the product velocity distributions in crossed molecular beam experiments. While maintaining conventional two-dimension velocity mapping, the third velocity component was mapped linearly to the ion time of flight. A weak extraction field was used to spread the ion turnaround time to several hundred nanoseconds, which permits good resolution for selection of the longitudinal velocity. A fast gated (⩾5 ns) intensified charge coupled device camera was used to record time-sliced ion images. Calibration of the apparatus was done by measuring O+ images from the multiphoton dissociation/ionization of O2. The resolution in velocity achieved was about 1% (Δv/v) in slicing through the center of a Newton sphere. The overall performance was examined by observing product ion images from the F+CD4→DF+CD3 reaction. To detect CD3+ with kinetic energy release of about 1 eV, 50 ns time slicing provides sufficient velocity resolution, such that res...
TL;DR: In this paper, Chandra spectra of the south east shell of SN 1006 were obtained from thermal emission in the shell with the excellent spatial resolution of Chandra and fitted with a thin thermal plasma of kT = 0.24 keV in non-equilibrium ionization (NEI).
Abstract: The north east shell of SN 1006 is the most probable acceleration site of high energy electrons (up to ~ 100 TeV) with the Fermi acceleration mechanism at the shock front. We resolved non-thermal filaments from thermal emission in the shell with the excellent spatial resolution of Chandra. The thermal component is extended widely over about ~ 100 arcsec (about 1 pc at 1.8 kpc distance) in width, consistent with the shock width derived from the Sedov solution. The spectrum is fitted with a thin thermal plasma of kT = 0.24 keV in non-equilibrium ionization (NEI), typical for a young SNR. The non-thermal filaments are likely thin sheets with the scale widths of ~ 4 arcsec (0.04 pc) and ~ 20 arcsec (0.2 pc) at upstream and downstream, respectively. The spectra of the filaments are fitted with a power-law function of index 2.1--2.3, with no significant variation from position to position. In a standard diffusive shock acceleration (DSA) model, the extremely small scale length in upstream requires the magnetic field nearly perpendicular to the shock normal. The injection efficiency (eta) from thermal to non-thermal electrons around the shock front is estimated to be ~ 1e-3 under the assumption that the magnetic field in upstream is 10 micro G. In the filaments, the energy densities of the magnetic field and non-thermal electrons are similar to each other, and both are slightly smaller than that of thermal electrons. in the same order for each other. These results suggest that the acceleration occur in more compact region with larger efficiency than previous studies.
TL;DR: In this paper, a numerical model of the negative DC corona plasma along a thin wire in dry air is presented, and the electron number density and electric field are determined from solution of the one-dimensional coupled continuity equations of charge carriers and Maxwell's equation.
Abstract: A numerical model of the negative DC corona plasma along a thin wire in dry air is presented. The electron number density and electric field are determined from solution of the one-dimensional coupled continuity equations of charge carriers and Maxwell's equation. The electron kinetic energy distribution is determined from the spatially homogeneous Boltzmann equation. A parametric study is conducted to examine the effects of linear current density (0.1–100 μA per cm of wire length), wire radius (10–1000 μm), and air temperature (293–800 K) on the distribution of electrons and the Townsend second ionization coefficient. The results are compared to those previously determined for the positive corona discharge. In the negative corona, energetic electrons are present beyond the ionization boundary and the number of electrons is an order of magnitude greater than in the positive corona. The number of electrons increases with increasing gas temperature. The electron energy distribution does not depend on discharge polarity.
TL;DR: In this article, the authors presented a detailed model for the ionized absorbing gas evident in the 900 ks Chandra HETGS spectrum of NGC 3783, which is well fitted by PHASE with just six free parameters.
Abstract: We present a detailed model for the ionized absorbing gas evident in the 900 ks Chandra HETGS spectrum of NGC 3783. The analysis was carried out with PHASE, a new tool designed to model X-ray and UV absorption features in ionized plasmas. The 0.5-10 keV intrinsic continuum of the source is well represented by a single power law (Γ = 1.53) and a soft blackbody component (kT ~ 0.1 keV). The spectrum contains over 100 features, which are well fitted by PHASE with just six free parameters. The model consists of a simple two-phase absorber with a difference of ≈35 in the ionization parameter and a difference of ≈4 in the column density of the phases. The two absorption components turned out to be in pressure equilibrium and are consistent with a single outflow (≈750 km s-1), a single turbulent velocity (300 km s-1), and solar elemental abundances. The main features of the low-ionization phase are an Fe M-shell unresolved transition array (UTA) and the O VII lines. The O VII features, usually identified with the O VIII and a warm absorber, are instead produced in a cooler medium that also produces O VI lines. The UTA sets tight constraints on the ionization degree of the absorbers, making the model more reliable. The high-ionization phase is required by the O VIII and the Fe L-shell lines, and there is evidence for an even more ionized component in the spectrum. A continuous range of ionization parameters is disfavored by the fits, particularly to the UTA. Our model indicates a severe blending of the absorption and emission lines, as well as strong saturation of the most intense O absorption lines. This is in agreement with the O VII (τλ = 0.33) and O VIII (τλ = 0.13) absorption edges required to fit the spectrum. The low-ionization phase can be decomposed into three subcomponents on the basis of the outflow velocity, FWHM, and H column densities found for three of the four UV absorbers detected in NGC 3783. However, the ionization parameters are systematically smaller in our model than those derived from UV data, indicating a lower degree of ionization. Finally, our model predicts a Ca XVI line for the feature observed at around 21.6 A (a feature formerly identified as O VII), constraining the contribution from a zero-redshift absorber.
TL;DR: In this article, a model of massive star formation by continuing accretion predicts a new class of gravitationally-trapped, long-lived hypercompact HII regions, where the momentum of the accretion flow is sufficient to push the dust grains through a narrow zone of high dust opacity at the ionization boundary.
Abstract: The formation of massive stars may take place at relatively low accretion rates over a long period of time if the accretion can continue past the onset of core hydrogen ignition. The accretion may continue despite the formation of an ionized HII region around the star if the HII region is small enough that the gravitational attraction of the star dominates the thermal pressure of the HII region. The accretion may continue despite radiation pressure acting against dust grains in the molecular gas if the momentum of the accretion flow is sufficient to push the dust grains through a narrow zone of high dust opacity at the ionization boundary and into the HII region where the dust is sublimated. This model of massive star formation by continuing accretion predicts a new class of gravitationally-trapped, long-lived hypercompact HII regions. The observational characteristics of the trapped hypercompact HII regions can be predicted for comparison with observations.
TL;DR: In this article, the authors presented distorted-wave calculations and analytic fits to the DR rate coefficients of H-like to Ne-like isosequences of seven abundant astrophysical elements, including Mg, Si, S, Ar, Ca, Fe, and Ni.
Abstract: We present distorted-wave calculations and analytic fits to the dielectronic recombination (DR) rate coefficients of H-like to Ne-like isosequences of seven abundant astrophysical elements, including Mg, Si, S, Ar, Ca, Fe, and Ni. Both ΔN = 0 (low-temperature) and ΔN > 0 (high-temperature) DR channels are included for L-shell ions. Values of ΔN > 0 DR for less abundant ions between Mg and Ni are also obtained through interpolation along the isosequences. Interpolation is not performed for ΔN = 0 DR, since such rate coefficients are not smooth along the isosequences in general. Comparison is made with existing theoretical and experimental results, and collisional ionization equilibria resulting from the current DR rate coefficients are presented.
TL;DR: In this paper, an IP-EOM coupled cluster (CC) method with full inclusion of the connected triple excitations for ionization energies has been formulated and implemented using proper factorization of the three-and four-body parts of the effective Hamiltonian.
Abstract: The equation-of-motion (EOM) coupled cluster (CC) method with full inclusion of the connected triple excitations for ionization energies has been formulated and implemented. Using proper factorization of the three- and four-body parts of the effective Hamiltonian, an efficient computational procedure has been proposed for IP-EOM-CCSDT which at the EOM level requires no-higher-than nocc3nvir4 scaling. The method is calibrated by the evaluation of the valence vertical ionization potentials for CO, N2, and F2 molecules for several basis sets up to 160 basis functions. At the basis set limit, errors vary from 0.0 to 0.2 eV, compared to “experimental” vertical ionization potentials.
TL;DR: In this paper, the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method is applied to the ionization of one-dimensional model molecules with up to eight active electrons.
Abstract: We introduce the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method and discuss significant differences to time-dependent density functional theory. The method is applied to the ionization of one-dimensional model molecules with up to eight active electrons. Correlation significantly influences both ground-state electron densities and ionization yields. In accordance with expectations, for constant ionization potential we find an increase of ionization yields with molecular size.
TL;DR: Replicate measurements made on known standards and seawater samples demonstrate that the analytical precision approximates that expected from counting statistics and that, based on detection limits of 38 and 49 ag, protactinium can be detected in a minimum sample size of surface seawater.
Abstract: A technique has been developed to quantify ultratrace 231Pa (50−2000 ag; 1 ag = 10-18 g) concentrations in seawater using isotope-dilution thermal ionization mass spectrometry (TIMS). The method is a modification of a process developed by Pickett et al. (Pickett, D. A.; Murrell, M. T.; Williams, R. W. Anal. Chem. 1994, 66, 1044−1049) and extends the technique to very low levels of protactinium. The procedural blank is 16 ± 15 ag (2σ), and the ionization efficiency (ions generated/atom loaded) approaches 0.5%. Measurement time is <1 h. The amount of 231Pa needed to produce 231Pa data with an uncertainty of ±4−12% is 100−1000 ag (∼3 × 105 to 3 × 106 atoms). Replicate measurements made on known standards and seawater samples demonstrate that the analytical precision approximates that expected from counting statistics and that, based on detection limits of 38 and 49 ag, protactinium can be detected in a minimum sample size of surface seawater of ∼2 L for suspended particulate matter and <0.1 L for filtered (<...
TL;DR: In this paper, the authors discuss optimal detection of fast radio transients from astrophysical objects while taking into account the effects of propagation through intervening ionized media, including dispersion, scattering and scintillation.
Abstract: We discuss optimal detection of fast radio transients from astrophysical objects while taking into account the effects of propagation through intervening ionized media, including dispersion, scattering and scintillation.Our analysis applies to the giant-pulse phenomenon exhibited by some pulsars, for which we show examples, and to radio pulses from other astrophysical sources, such as prompt radio emission from gamma-ray burst sources and modulated signals from extra-terrestrial civilizations.
TL;DR: It is shown that pKa values accurate enough for identifying the proton donor in an enzyme active site can be calculated by considering in detail only the active‐site residues and their immediate electrostatic interaction partners, thus allowing for a large decrease in calculation time.
Abstract: The ionization properties of the active-site residues in enzymes are of considerable interest in the study of the catalytic mechanisms of enzymes. Knowledge of these ionization constants (pKa values) often allows the researcher to identify the proton donor and the catalytic nucleophile in the reaction mechanism of the enzyme. Estimates of protein residue pKa values can be obtained by applying pKa calculation algorithms to protein X-ray structures. We show that pKa values accurate enough for identifying the proton donor in an enzyme active site can be calculated by considering in detail only the active-site residues and their immediate electrostatic interaction partners, thus allowing for a large decrease in calculation time. More specifically we omit the calculation of site-site interaction energies, and the calculation of desolvation and background interaction energies for a large number of pairs of titratable groups. The method presented here is well suited to be applied on a genomic scale, and can be implemented in most pKa calculation algorithms to give significant reductions in calculation time with little or no impact on the accuracy of the results. The work presented here has implications for the understanding of enzymes in general and for the design of novel biocatalysts.
TL;DR: A glow discharge spectroscopy (GDS) source operates at atmospheric pressure as discussed by the authors, where one of the discharge electrodes of the device is formed by an electrolytic solution 27 containing the analyte specimen.
Abstract: A glow discharge spectroscopy (GDS) source operates at atmospheric pressure. One of the discharge electrodes of the device is formed by an electrolytic solution 27 containing the analyte specimen. The passage of electrical current (either electrons or positive ions) across the solution/gas phase interface causes local heating and the volatilization of the analyte species. Collisions in the discharge region immediately above the surface of the solution results in optical emission and ionization that are characteristic of the analyte elements. As such, these analyte elements can be identified and quantified by optical emission spectroscopy (OES) or mass spectrometry (MS). The device uses the analyte solution as either the cathode or anode. Operating parameters depend on the electrolyte concentration (i.e. solution conductivity) and the gap 35 between the solution surface and the counter electrode. Typical conditions include discharge currents of about 10 to about 60 mA and potentials of about 200 to about 1000 volts. Electrolyte solutions of pH, pNa or pLi values of about 0.5 to about 2 and interelectrode gaps of about 0.5 to about 3 mm produce stable plasmas where the analyte solutions are totally consumed at flow rates of up to about 2.0 mL/min.
TL;DR: In this article, a long 280 ks observation of the Seyfert 1 galaxy NGC 3783 with XMM-Newton is reported, where the authors focus on the oxygen line complex between 17 and 24 A as measured with the RGS spectrometers.
Abstract: A long 280 ks observation of the Seyfert 1 galaxy NGC 3783 with XMM-Newton is reported. We focus on the oxygen line complex between 17 and 24 A as measured with the RGS spectrometers. Accurate absorption column densities and emission line fluxes are obtained. We explore several options for the geometry and physical form of the emitting and absorbing gas. The lack of change in ionization in the absorber despite an increase in continuum flux during the observation restricts the high-ionization (O-K) and the low-ionization (Fe-M) gas to distances of at least 0.5 pc and 2.8 pc, respectively, away from the central source. Given the P-Cygni type profiles in the resonance spectral lines and the similar velocity widths, column densities, and ionization structure inferred separately from the emission and absorption lines, it is tempting to relate the X-ray narrow-line emitting plasma with the X-ray absorbing gas. Under this assumption, the scenario of dense clumped clouds can be ruled out. Conversely, extended ionization cones (r > 10 pc) are consistent with the observation independent of this assumption. These findings are in stark contrast with the picture of numerous clumpy (n_e > 10^9 cm^-3) clouds drawn recently from UV spectra, but it is consistent with the extended X-ray emission cones observed directly in Seyfert 2 galaxies.
TL;DR: A novel ion source based on the principle of sonic spray ionization has been built and used to optimize mass spectrometric conditions for generating amino acid clusters, with a strong chiral preference in favor of homochiral cluster formation in the cases of threonine and cysteine.
Abstract: A novel ion source based on the principle of sonic spray ionization has been built and used to optimize mass spectrometric conditions for generating amino acid clusters. The ion source employs a simple pneumatic spray operated at extremely high nebulizing gas flow rates. Several factors that affect the performance of the cluster source are identified, and information from these observations provides insights into the mechanisms of gas phase ion formation. Serine is used as a model system in optimizing instrumental and sample parameters to maximize cluster ion formation. The sonic spray results for this oligomer compare favorably with electrospray data, showing an order of magnitude better signal intensity and excellent signal-to-noise ratios. The performance of the system for the protonated serine octamer includes a limit of detection of 10 nM and a linear dynamic range of 4 orders of magnitude. Ion formation was observed to go into saturation above 1 mM. This result and data on pH, electrolyte concentration, and solvent composition are interpreted as supporting a charge residue model of sonic spray ionization. Other amino acids can be substituted for serine in the octamer, with a strong chiral preference in favor of homochiral cluster formation in the cases of threonine and cysteine. These amino acids show a preference for substitution of more than two serine molecules. Phenylalanine, asparagine, tryptophan, and tyrosine also substitute into the serine octamer; however, the process yields only two incorporations and only small chiral effects.
TL;DR: In this article, a one-dimensional axial model of a Hall thruster discharge through source terms obtained from an auxiliary model of the radial dynamics is presented. And the acceleration is set by the balance between gas ionization and wall recombination in the acceleration region.
Abstract: The interaction of the plasma discharge with the ceramic walls of a Hall thruster leads to plasma recombination, energy losses, and extra electron collisionality. These three phenomena are included in a one-dimensional axial model of the discharge through source terms obtained from an auxiliary model of the radial dynamics. Spatial solutions are presented for different discharge voltages and wall materials, and agree satisfactorily with experimental data. The parameters related to wall effects are investigated extensively. The energy balance among Joule heating, wall-losses cooling, and heat conduction shapes the temperature profile; three different profile types are identified depending on the wall material and the discharge voltage. For long chambers, the main source of energy losses is the plasma interaction with the walls, even for zero secondary electron emission. By contrast, wall collisionality due to primary/secondary exchanges of electrons is negligible always. The current utilization is related directly to the total energy losses. The propellant utilization is set by the balance between gas ionization and wall recombination in the acceleration region. The rate of wall recombination suggested by the axial solution is much lower than the values given by radial models based on a Maxwellian electron distribution function.
TL;DR: In this paper, the authors report on the observation of O VII Doppler line broadening in a compact knot at the edge of SN 1006 detected with the reflective grating spectrometer on board XMM-Newton.
Abstract: We report on the observation of O VII Doppler line broadening in a compact knot at the edge of SN 1006 detected with the reflective grating spectrometer on board XMM-Newton. The observed line width of σ = 3.4 ± 0.5 eV at a line energy of 574 eV indicates an oxygen temperature of kT = 528 ± 150 keV. Combined with the observed electron temperature of ~1.5 keV, the observed broadening is direct evidence for temperature nonequilibration in high Mach number shocks and slow subsequent equilibration. The O VII line emission allows an accurate determination of the ionization state of the plasma, which is characterized by a relatively high forbidden line contribution, indicating log net 9.2.
TL;DR: In this article, non-LTE line formation calculations of Fei are performed for a small number of reference stars to investigate and quantify the eciency of neutral hydrogen collisions, based on the assumption that the surface gravities as determined by the Fei/Feii ionization equilibria are in agreement with their astrometric counterparts obtained from Hipparcos parallaxes.
Abstract: Non-LTE line formation calculations of Fei are performed for a small number of reference stars to investigate and quantify the eciency of neutral hydrogen collisions. Using the atomic model that was described in previous publications, the final discrimination with respect to hydrogen collisions is based on the condition that the surface gravities as determined by the Fei/Feii ionization equilibria are in agreement with their astrometric counterparts obtained from Hipparcos parallaxes. High signal-to-noise, high-resolutionspectra are analysed to determine individual profile fits and di erential abundances of iron lines. Depending on the choice of the hydrogen collision scaling factor S H, we find deviations from LTE in Fe i ranging from 0.00 (S H=1 )t o 0.46 dex (S H= 0 for HD 140283) in the logarithmic abundances while Feii follows LTE. With the exception of Procyon, for which a mild temperature correction is needed to fulfil the ionization balance, excellent consistency is obtained for the metal-poor reference stars if Balmer profile temperatures are combined with S H= 3. This value is much higher than what is found for simple atoms like Li or Ca, both from laboratory measurements and inference of stellar analyses. The correct choice of collisional damping parameters ("van-der-Waals" constants) is found to be generally more important for these little evolved metal-poor stars than considering departures from LTE. For the Sun the calibrated value for S H leads to average Fei non-LTE corrections of 0.02 dex and a mean abundance from Fei lines of log"(Fe)= 7.49 0.08. We confront the deduced stellar parameters with comparable spectroscopic analyses by other authors which also rely on the iron ionization equilibrium as a gravity indicator. On the basis of the Hipparcos astrometry our results are shown to be an order of magnitude more precise than published data sets, both in terms of oset and star-to-star scatter.
TL;DR: It was found that the high-mass regions of the ME-SIMS spectra closely resembled those obtained using matrix-assisted laser desorption/ionization (MALDI), and imaging SIMS was found to be a versatile tool to investigate the effects of the local physicochemical conditions on the detected molecular species.
Abstract: Intense intact molecular ion signals have been obtained from phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, and phosphatidylinositol using matrix-enhanced secondary ion mass spectrometry (ME-SIMS). It was found that the high-mass (m/z >500) regions of the ME-SIMS spectra closely resembled those obtained using matrix-assisted laser desorption/ionization (MALDI). Using high spatial resolution SIMS, a detailed investigation of dried-droplet samples was performed. Based on the detected Na+ and 2,5-DHB matrix signal intensities, different crystal types were distinguished, in addition to different sizes of crystals. Spatially mapping the pseudomolecular and fragment ions of the phospholipids revealed that the nature of the pseudomolecular ions formed, as well as the ratio of intact molecular to fragment ion, was dependent on the type and surface composition of the crystal. The observed chemical bias effects due to crystal heterogeneity and the resulting variation in desorption/ionization e...
TL;DR: In this paper, the optimized structure and electronic properties of neutral and singly charged magnesium clusters have been investigated using ab initio theoretical methods based on density-functional theory and systematic post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system.
Abstract: The optimized structure and electronic properties of neutral and singly charged magnesium clusters have been investigated using ab initio theoretical methods based on density-functional theory and systematic post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system. We have systematically calculated the optimized geometries of neutral and singly charged magnesium clusters consisting of up to 21 atoms, electronic shell closures, binding energies per atom, ionization potentials, and the gap between the highest occupied and the lowest unoccupied molecular orbitals. We have investigated the appearance of the elements of the hcp structure and metallic evolution of the magnesium clusters, as well as the stability of linear chains and rings of magnesium atoms. The results obtained are compared with the available experimental data and the results of other theoretical works.
TL;DR: In this article, the authors derived the breakdown field for the onset of corona as a function of the radius of the sphere, which is similar to, but different from, Peek's formula for the early onset for cylinders or wires.
Abstract: Predictions are made of the electric field necessary for the onset of corona in air for spheres and cylinders from the general breakdown criterion, ; α' is the net ionization coefficient, r is the radius and Q is a constant. It is found that Q = 104 gives a fair fit to experimental results for both wires and points, and for positive and negative corona, for radii varying from 0.01 to 20 cm. By assuming a linear variation of α' with the difference of the electric field from the critical field where ionization equals attachment, an analytic formula can be derived for the breakdown field for the onset of corona as a function of the radius of the sphere, which is similar to, but different from, Peek's formula for the onset of corona for cylinders or wires. The formulae also give the breakdown field as a function of temperature and pressure. For Townsend and Streamer breakdown mechanisms, values of Q are typically 3 × 104 and 108, respectively. Thus the value of Q derived from experimental values of the onset field for corona for both wires and points is significantly lower than would be expected from either the Townsend breakdown criterion or the Streamer breakdown criterion. It is suggested that the most likely collision process to explain the observed low value of Q is indirect ionization, for example by collisions between excited molecules.
TL;DR: Deleuze et al. as discussed by the authors presented a benchmark theoretical determination of the ionization thresholds of polycyclic aromatic compounds within chemical accuracy [0.02-0.07 eV].
Abstract: In straightforward continuation of Green’s function studies of the ultraviolet photoelectron spectra of polycyclic aromatic compounds [Deleuze et al., J. Chem. Phys. 115, 5859 (2001); M. S. Deleuze, ibid. 116, 7012 (2002)], we present a benchmark theoretical determination of the ionization thresholds of benzene, naphthalene, anthracene, naphthacene (tetracene), pentacene, and hexacene, within chemical accuracy [0.02–0.07 eV]. The vertical ionization potentials of these compounds have been obtained from series of single-point calculations at the Hartree–Fock, second-, third-, and partial fourth-order Moller–Plesset (MP2, MP3, MP4SDQ) levels, and from coupled cluster calculations including single and double excitations (CCSD) as well as a perturbative estimate of connected triple excitations [CCSD(T)], using basis sets of improving quality, introducing up to 510, 790, 1070, 1350, 1630, and 1910 basis functions in the computations, respectively. A focal point analysis of the convergence of the calculated ionization potentials has been performed in order to extrapolate the CCSD(T) results to an asymptotically (cc-pV∞Z) complete basis set. The present results confirm the adequacy of the outer-valence Green’s function scheme for strongly correlated systems. Adiabatic ionization energies have been further determined by incorporating Beck-three-parameter Lee–Yang–Parr functional corrections for zero-point vibrational energies and for geometrical relaxations. Extension of the analysis to the CCSD(T)/cc-pV∞Z level shows that the energy minimum form of the benzene radical cation is an obtuse structure related to the 2B2g state. Isotopic shifts of the adiabatic ionization potentials, due to deuterium substitution of hydrogens, have also been discussed.
TL;DR: This work studied multiple ionization of single nucleobases by means of slow highly charged ions (Xe(q+), q=5-25) to shed light on the charge distribution within the molecule and on the fragmentation dynamics of these intermediate size systems.
Abstract: We studied multiple ionization of single nucleobases by means of slow highly charged ions (${\mathrm{X}\mathrm{e}}^{q+}$, $q=5--25$). The products of the subsequent fragmentation were studied using high resolution coincidence time-of-flight spectrometry. We observed a strong dependence of the fragment kinetic energies on the initial charge state of the intermediate parent ions as well as on the initial chemical environment of the respective fragment ions within the parent molecule. The data allow us to shed light on the charge distribution within the molecule as well as on the fragmentation dynamics of these intermediate size systems.
TL;DR: In this article, the authors compared molecular-line emission to dust continuum emission and modeled molecular lines using Monte Carlo simulations in order to study the depletion of molecules and the ionization fraction in three pre-protostellar cores, L1512, L 1544, and L1689B.
Abstract: We have compared molecular-line emission to dust continuum emission and modeled molecular lines using Monte Carlo simulations in order to study the depletion of molecules and the ionization fraction in three pre-protostellar cores, L1512, L1544, and L1689B. L1512 is much less dense than L1544 and L1689B, which have similar density structures. L1689B has a different environment from those of L1512 and L1544. We used density and temperature profiles, calculated by modeling dust continuum emission in the submillimeter, for modeling molecular-line profiles. In addition, we have used molecular-line profiles and maps observed in several different molecules toward the three cores. We find a considerable diversity in chemical state among the three cores. The molecules include those sensitive to different timescales of chemical evolution such as CCS, the isotopes of CO and HCO+, DCO+, and N2H+. The CO molecule is significantly depleted in L1512 and L1544 but not in L1689B. CCS may be in the second enhancement of its abundance in L1512 and L1544 because of the significant depletion of CO molecules. N2H+ might already be starting to be depleted in L1512, but it traces very well the distribution of dust emission in L1544. On the other hand, L1689B may be so young that N2H+ has not reached its maximum yet. The ionization fraction has been calculated using H13CO+ and DCO+. The result shows that the ionization fraction is similar toward the centers of the three cores. This study suggests that chemical evolution depends on the absolute timescale during which a core stays in a given environment as well as its density structure.