scholarly journals Astrochemical relevance of VUV ionization of large PAH cations

2020 ◽  
Vol 641 ◽  
pp. A98 ◽  
Author(s):  
G. Wenzel ◽  
C. Joblin ◽  
A. Giuliani ◽  
S. Rodriguez Castillo ◽  
G. Mulas ◽  
...  
Keyword(s):  
Cross Sections ◽  
Density Functional ◽  
Interstellar Dust ◽  
Vacuum Ultraviolet ◽  
Branching Ratio ◽  
Molecular Size ◽  
Photoelectric Effect ◽  
Interstellar Gas ◽  
Ionization Cross Sections ◽  
The Impact

Context. As part of interstellar dust, polycyclic aromatic hydrocarbons (PAHs) are processed by an interaction with vacuum ultraviolet (VUV) photons emitted by hot stars. This interaction leads to the emission of not only the well-known aromatic infrared bands, but also electrons, which can significantly contribute to the heating of the interstellar gas. Aims. Our aim is to investigate the impact of molecular size on the photoionization properties of cationic PAHs. Methods. Trapped PAH cations of sizes between 30 and 48 carbon atoms were submitted to VUV photons in the range of 9–20 eV from the DESIRS beamline at the synchrotron SOLEIL. All resulting photoproducts including dications and fragment cations were mass-analyzed and recorded as a function of photon energy. Results. Photoionization is found to be predominant over dissociation at all energies, which differs from the conclusions of an earlier study on smaller PAHs. The photoionization branching ratio reaches 0.98 at 20 eV for the largest studied PAH. The photoionization threshold is observed to be between 9.1 and 10.2 eV, in agreement with the evolution of the ionization potential with size. Ionization cross sections were indirectly obtained and photoionization yields extracted from their ratio with theoretical photoabsorption cross sections, which were calculated using time-dependent density functional theory. An analytical function was derived to calculate this yield for a given molecular size. Conclusions. Large PAH cations could be efficiently ionized in H I regions and contribute to the heating of the gas by the photoelectric effect. Also, at the border of or in H II regions, PAHs could be exposed to photons of energy higher than 13.6 eV. Our work provides recipes to be used in astronomical models to quantify these points.

scholarly journals Pyr1,xTFSI Ionic Liquids (x = 1–8): A Computational Chemistry Study

2020 ◽  
Vol 10 (23) ◽  
pp. 8552
Author(s):  
Sergio Brutti
Keyword(s):  
Ionic Liquids ◽  
Physicochemical Properties ◽  
Density Functional ◽  
Ion Pairs ◽  
Molecular Size ◽  
Molecular Structures ◽  
Safety Standards ◽  
Oxidation Reduction ◽  
Reduction Stability ◽  
The Impact

Pyrrolidinium-based (Pyr) ionic liquids are a very wide family of molecular species. Pyrrolidinium cations are electrochemically stable in a large potential interval and their molecular size hinders their transport properties. The corresponding ionic liquids with trifluoromethyl sulphonyl imide anions are excellent solvents for lithium/sodium salts and have been demonstrated as electrolytes in aprotic batteries with enhanced safety standards. In this study, the analysis of the physicochemical properties of a homologous series of pyrrolidinium-based ionic liquids with general formula Pyr1,xTFSI (x = 1–8) have been tackled by first principles calculations based on the density functional theory. The molecular structures of isolated ions and ion pairs have been predicted by electronic structure calculations at B3LYP level of theory in vacuum or in simulated solvents. Thermodynamic properties have been calculated to evaluate the ion pairs dissociation and oxidation/reduction stability. This is the first systematic computational analysis of this series of molecules with a specific focus on the impact of the length of the alkyl chain on the pyrrolidinium cation on the overall physicochemical properties of the ion pairs.

Cosmic-ray nuclei up to 10 10 eV/u in the galaxy

1975 ◽  
Vol 277 (1270) ◽  
pp. 319-348 ◽  
Keyword(s):  
Cosmic Rays ◽  
Solar System ◽  
Cross Sections ◽  
Cosmic Ray ◽  
Interstellar Space ◽  
Heavy Nuclei ◽  
Hydrogen Atoms ◽  
Interstellar Gas ◽  
The Galaxy ◽  
Ionization Cross Sections

O f the nuclear cosmic rays arriving in the vicinity of Earth from interstellar space, more than 90% have energies less than 1010 eV /u.f Some effects of their modulation (including deceleration) in the Solar System are briefly discussed. The origin of particles at energies < 107 eV/u is still obscure. They could be due to stellar explosions or to solar emissions, or perhaps to interaction of interstellar gas with the solar wind. Between 108 and 1010 eV/u, the composition appears constant to ca. 30% within the statistics of available data. Cosmic rays traverse a mean path length of 6 g/cm 2 in a medium assumed to contain nine hydrogen atoms for each helium atom. Spallation reactions occurring in this medium result in enhancement of many cosmic-ray elements that are more scarce in the general abundances by several orders of magnitude. Cosmic-ray dwell time in the Galaxy seems to be < 107 years. The source composition of cosmic rays has been derived for elements with atomic numbers 1 ≤ Z ≤ 26. A comparison with abundances in the Solar System implies that the latter is richer in hydrogen and helium by a factor of ca. 20, in N and O by ca. 5, and in C by a factor of ca.2. Possible interpretations invoke (a) nucleosynthesis of cosmic rays in certain sources, e.g. supernovae, or (b) models of selective injection that depend, e.g. on ionization potentials or ionization cross sections. Calculated isotopic abundances of arriving cosmic rays are compared with the observed values now becoming available, and found to be in general agreement. Recent progress in probing the composition and spectrum of ultra-heavy nuclei is outlined.

scholarly journals Comprehensive investigation of the electronic excitation of W(CO)6 by photoabsorption and theoretical analysis in the energy region from 3.9 to 10.8 eV

2017 ◽  
Vol 8 ◽  
pp. 2208-2218 ◽  
Author(s):  
Mónica Mendes ◽  
Khrystyna Regeta ◽  
Filipe Ferreira da Silva ◽  
Nykola C Jones ◽  
Søren Vrønning Hoffmann ◽  
...  
Keyword(s):  
Electron Scattering ◽  
Cross Sections ◽  
Lower Energy ◽  
Density Functional ◽  
Vacuum Ultraviolet ◽  
Energy Bands ◽  
Ligand Charge Transfer ◽  
Comprehensive Knowledge ◽  
Relativistic Time ◽  
Electronically Excited

High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115–320 nm (10.8–3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO)6. The higher resolution obtained reveals previously unresolved spectral features of W(CO)6. The spectrum shows two higher-energy bands (in the energy ranges of 7.22–8.12 eV and 8.15–9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin–orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO)6, a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements.

scholarly journals Optical and Radio Information

1968 ◽  
Vol 1 ◽  
pp. 206-209
Author(s):  
Hugh M. Johnson
Keyword(s):  
Cross Sections ◽  
Supernova Remnants ◽  
Galactic Plane ◽  
Optical Data ◽  
X Rays ◽  
Interstellar Gas ◽  
X Ray ◽  
The Galaxy ◽  
Ionization Cross Sections ◽  
Optical Astronomy

The six or eight optically identified X-ray sources comprise starlike objects and extended supernova remnants in the Galaxy, well as as a radio galaxy and a quasar. Both X-ray and radiofrequency radiation penetrate the entire galactic plane, but only two or three galactic radio sources have been identified with X-ray sources. This has led Hayakawa et al. to postulate that detectable X-ray sources are not farther than 1 kpc. However, other studies suggest that there is a cluster of a few intrinsically bright sources actually near the galactic nucleus and a scattering of weaker sources near the sun.The distances of X-ray sources can be estimated from extinction by interstellar gas or intergalactic gas on spectra above 10 Å, but the method ultimately depends on the radio and optical data of the gas. Conversely, interstellar densities of certain elements with large photo-ionization cross-sections may be determined from the absorption of X-rays, after calibration of source distances by the methods of optical astronomy.

scholarly journals Pygmy and giant resonances: connecting the nuclear structure to stellar astrophysics

2018 ◽  
Vol 194 ◽  
pp. 04001
Author(s):  
Nadia Tsoneva
Keyword(s):  
Cross Sections ◽  
Density Functional ◽  
Reaction Cross ◽  
Giant Resonances ◽  
Energy Density Functional ◽  
Theoretical Investigations ◽  
Dipole Response ◽  
The Impact ◽  
Reaction Cross Sections ◽  
Phonon Model

Systematic theoretical investigations of dipole response in neutron-rich nuclei of importance for day-one photonuclear experiments at ELI-NP are presented. The calculations are performed in advanced mi- croscopic theory based on energy-density functional and three-phonon quasiparticle-phonon model. The model basis accounts for a large range of nuclear excitations with different spin and parity. In the focus of the studies are electric and magnetic dipole modes with energies up to 25 MeV. Of special interest are pygmy dipole and giant dipole resonances. The impact of different low-energy excitations and in particular of the PDR on radia- tive neutron-capture reaction cross sections in nuclei of key importance for nucleosynthesis is investigated.The obtained results are compared to available experimental data.

scholarly journals Energy Dependency of Proton-Induced Outer-Shell Multiple Ionization for 48Cd and 49In

2021 ◽  
Vol 2021 ◽  
pp. 1-7
Author(s):  
Xianming Zhou ◽  
Jing Wei ◽  
Rui Cheng ◽  
Yanhong Chen ◽  
Yongtao Zhao ◽  
...  
Keyword(s):  
Cross Sections ◽  
Relative Intensity ◽  
Outer Shell ◽  
Atomic Data ◽  
X Rays ◽  
X Ray ◽  
Direct Ionization ◽  
Multiple Ionization ◽  
Ionization Cross Sections ◽  
The Impact

L subshell X-rays of 48Cd and 49In have been measured for the impact of protons with energies from 75 to 250 keV. Obviously, it is found that Lγ2 (abbreviation Lγ2,3 for 48Cd and Lγ2,3,4 for 49In) X-ray emission is enhanced in comparison with Lγ1 X-ray emission. The relative intensity ratios of Lγ2 to Lγ1 X-ray are larger than the atomic data and increase with decreasing proton energy. This is caused by the multiple ionization of outer-shell electrons. To verify this explanation, the enhancements for relative intensity ratio of Lι and Lβ2 to Lα X-ray in experiments are discussed, and the direct ionization cross sections of 4d, 5s, and 5p electrons are calculated using BEA theory.

scholarly journals Excited States of Bromopyrimidines Probed by VUV Photoabsorption Spectroscopy and Theoretical Calculations

2021 ◽  
Vol 22 (12) ◽  
pp. 6460
Author(s):  
Mónica Mendes ◽  
Fábris Kossoski ◽  
Ana I. Lozano ◽  
João Pereira-da-Silva ◽  
Rodrigo Rodrigues ◽  
...  
Keyword(s):  
Absorption Band ◽  
Cross Sections ◽  
Density Functional ◽  
Vacuum Ultraviolet ◽  
Theoretical Calculations ◽  
Broad Band ◽  
Rydberg States ◽  
Detailed Comparison ◽  
Absorption Data ◽  
Franck Condon

We report absolute photoabsorption cross sections for gas-phase 2- and 5-bromopyrimidine in the 3.7–10.8 eV energy range, in a joint theoretical and experimental study. The measurements were carried out using high-resolution vacuum ultraviolet synchrotron radiation, with quantum chemical calculations performed through the nuclear ensemble approach in combination with time-dependent density functional theory, along with additional Franck–Condon Herzberg–Teller calculations for the first absorption band (3.7–4.6 eV). The cross sections of both bromopyrimidines are very similar below 7.3 eV, deviating more substantially from each other at higher energies. In the 7.3–9.0 eV range where the maximum cross-section is found, a single and broad band is observed for 5-bromopyrimidine, while more discernible features appear in the case of 2-bromopyrimidine. Several π* ← π transitions account for the most intense bands, while weaker ones are assigned to transitions involving the nitrogen and bromine lone pairs, the antibonding σ*Br orbital, and the lower-lying Rydberg states. A detailed comparison with the available photo-absorption data of bromobenzene is also reported. We have found significant differences regarding the main absorption band, which is more peaked in bromobenzene, becoming broader and shifting to higher energies in both bromopyrimidines. In addition, there is a significant suppression of vibrational structures and of Rydberg states in the pair of isomers, most noticeably for 2-bromopyrimidine.

The efficiency of application of virtual cross-sections method and hypotheses MELS in problems of wave signal propagation in elastic waveguides with rough surfaces

2016 ◽  
pp. 3564-3575 ◽  
Author(s):  
Ara Sergey Avetisyan
Keyword(s):  
Half Space ◽  
Cross Sections ◽  
Classical Method ◽  
Signal Propagation ◽  
Elastic Half Space ◽  
Layered Systems ◽  
Surface Layers ◽  
Inhomogeneous Surface ◽  
Wave Signal ◽  
The Impact

The efficiency of virtual cross sections method and MELS (Magneto Elastic Layered Systems) hypotheses application is shown on model problem about distribution of wave field in thin surface layers of waveguide when plane wave signal is propagating in it. The impact of surface non-smoothness on characteristics of propagation of high-frequency horizontally polarized wave signal in isotropic elastic half-space is studied. It is shown that the non-smoothness leads to strong distortion of the wave signal over the waveguide thickness and along wave signal propagation direction as well.  Numerical comparative analysis of change in amplitude and phase characteristics of obtained wave fields against roughness of weakly inhomogeneous surface of homogeneous elastic half-space surface is done by classical method and by proposed approach for different kind of non-smoothness.

scholarly journals A note on the relations between elastic and inelastic interactions and increasing ratio σel(s)/σtot(s) at the LHC

2019 ◽  
Vol 34 (32) ◽  
pp. 1950259 ◽  
Author(s):  
S. M. Troshin ◽  
N. E. Tyurin
Keyword(s):  
Elastic Scattering ◽  
Energy Dependence ◽  
Impact Parameter ◽  
Cross Sections ◽  
Parameter Dependence ◽  
Slope Parameter ◽  
Short Notice ◽  
Inelastic Interactions ◽  
The Impact ◽  
Mode A

We comment briefly on relations between the elastic and inelastic cross-sections valid for the shadow and reflective modes of the elastic scattering. Those are based on the unitarity arguments. It is shown that the redistribution of the probabilities of the elastic and inelastic interactions (the form of the inelastic overlap function becomes peripheral) under the reflective scattering mode can lead to increasing ratio of [Formula: see text] at the LHC energies. In the shadow scattering mode, the mechanism of this increase is a different one, since the impact parameter dependence of the inelastic interactions probability is central in this mode. A short notice is also given on the slope parameter and the leading contributions to its energy dependence in both modes.

scholarly journals Combinations of Freeze-Dried Amorphous Vardenafil Hydrochloride with Saccharides as A Way to Enhance Dissolution Rate and Permeability

2021 ◽  
Vol 14 (5) ◽  
pp. 453
Author(s):  
Gabriela Wiergowska ◽  
Dominika Ludowicz ◽  
Kamil Wdowiak ◽  
Andrzej Miklaszewski ◽  
Kornelia Lewandowska ◽  
...  
Keyword(s):  
Physicochemical Properties ◽  
Density Functional ◽  
Hydroxypropyl Methylcellulose ◽  
Fold Increase ◽  
Crystalline Form ◽  
Amorphous Form ◽  
Freeze Dried ◽  
Apparent Solubility ◽  
Gastrointestinal Epithelium ◽  
The Impact

To improve physicochemical properties of vardenafil hydrochloride (VAR), its amorphous form and combinations with excipients—hydroxypropyl methylcellulose (HPMC) and β-cyclodextrin (β-CD)—were prepared. The impact of the modification on physicochemical properties was estimated by comparing amorphous mixtures of VAR to their crystalline form. The amorphous form of VAR was obtained as a result of the freeze-drying process. Confirmation of the identity of the amorphous dispersion of VAR was obtained through the use of comprehensive analysis techniques—X-ray powder diffraction (PXRD) and differential scanning calorimetry (DSC), supported by FT-IR (Fourier-transform infrared spectroscopy) coupled with density functional theory (DFT) calculations. The amorphous mixtures of VAR increased its apparent solubility compared to the crystalline form. Moreover, a nearly 1.3-fold increase of amorphous VAR permeability through membranes simulating gastrointestinal epithelium as a consequence of the changes of apparent solubility (Papp crystalline VAR = 6.83 × 10−6 cm/s vs. Papp amorphous VAR = 8.75 × 10−6 cm/s) was observed, especially for its combinations with β-CD in the ratio of 1:5—more than 1.5-fold increase (Papp amorphous VAR = 8.75 × 10−6 cm/s vs. Papp amorphous VAR:β-CD 1:5 = 13.43 × 10−6 cm/s). The stability of the amorphous VAR was confirmed for 7 months. The HPMC and β-CD are effective modifiers of its apparent solubility and permeation through membranes simulating gastrointestinal epithelium, suggesting a possibility of a stronger pharmacological effect.

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