Calibration of oxygen 1s ionization energies. Accurate energies for CO2, H2O, CO, and O2

Access to accurate reference data is a prerequisite in order to translate chemical shifts to an absolute scale for inner-shell ionization energies. Calibration standards for oxygen 1s (O 1s) ionization energies are less well established than, for instance, for carbon 1s. To improve upon this situation, adiabatic and vertical O 1s ionization energies for gaseous carbon dioxide (CO2) are critically reviewed and used to establish the most accurate values currently available: 541.085(17) and 541.253(17) eV, respectively. Combining these with new precise measurements of shifts in O 1s ionization energies for H2O, CO, and O2 allows us to establish equally accurate absolute ionization energies for these molecules as for CO2. The resulting adiabatic and vertical energies are 539.728(17) and 539.827(17) eV for H2O, 542.439(17) and 542.495(17) eV for CO, 543.285(17) and 543.294(17) eV for O2 (4Σ final state), and 544.338(17) and 544.423(17) eV for O2 (2Σ final state). It is proposed that O 1s in CO2 be adopted as a standard of higher precedence, and that H2O, CO, and O2 be used also. The O 1s ionization energies in these molecules occur in the range 540–543 eV. These proposed standards should provide optimal internal calibration for a wide range of oxygen-containing compounds.publishedVersio

Electronic Properties of Chlorine, Methyl, and Chloromethyl as Substituents to the Ethylene Group-Viewed from the Core of Carbon

“Substituent effects” is an important and useful concept in organic chemistry. Although there are many approaches to parametrizing the electronic and steric effects of substituents, the physical basis for the parameters is often unclear. The purpose of the present work is to explore the properties of chemical shifts in carbon 1s energies as a well-defined basis for characterizing substituents to an ethylene C═C moiety. To this end, high-resolution carbon 1s photoelectron spectra of six chloro-substituted ethenes and seven chloro-substituted propenes have been measured in the gas phase. Site-specific adiabatic ionization energies have been determined from the spectra using theoretical ab initio calculations to predict the vibrational structures. For two molecules, 3-chloropropene and 2,3-dichloropropene, the spectral analyses give quantitative results for the conformer populations. The observed shifts have been analyzed in terms of initial-state (potential) and relaxation effects, and charge relaxation has also been analyzed by means of natural resonance theory. On the basis of core-level spectroscopy and models, chlorine, methyl, and chloromethyl have been characterized in terms of their effect on the carbon to which they are attached (α site) as well as the neighboring sp² carbon (β site). The derived spectroscopic substituent parameters are characterized by both inductive (electronegativity) effects and the ability of each substituent to engage in electron delocalization via the π system. Moreover, the adopted approach is extended to include substituent–substituent interaction parameters

Magnetic field structure due to the global velocity field in spiral galaxies

We present a set of global, self-consistent N-body/SPH simulations of the dynamic evolution of galactic discs with gas and including magnetic fields. We have implemented a description to follow the evolution of magnetic fields with the ideal induction equation in the SPH part of the Vine code. Results from a direct implementation of the field equations are compared to a representation by Euler potentials, which pose a div(B)-free description, an constraint not fulfilled for the direct implementation. All simulations are compared to an implementation of magnetic fields in the Gadget code which includes also cleaning methods for div(B). Starting with a homogeneous seed field we find that by differential rotation and spiral structure formation of the disc the field is amplified by one order of magnitude within five rotation periods of the disc. The amplification is stronger for higher numerical resolution. Moreover, we find a tight connection of the magnetic field structure to the density pattern of the galaxy in our simulations, with the magnetic field lines being aligned with the developing spiral pattern of the gas. Our simulations clearly show the importance of non-axisymmetry for the evolution of the magnetic field.Comment: 17 pages, 18 figure

Excitation and relaxation in atom-cluster collisions

Electronic and vibrational degrees of freedom in atom-cluster collisions are treated simultaneously and self-consistently by combining time-dependent density functional theory with classical molecular dynamics. The gradual change of the excitation mechanisms (electronic and vibrational) as well as the related relaxation phenomena (phase transitions and fragmentation) are studied in a common framework as a function of the impact energy (eV...MeV). Cluster "transparency" characterized by practically undisturbed atom-cluster penetration is predicted to be an important reaction mechanism within a particular window of impact energies.Comment: RevTeX (4 pages, 4 figures included with epsf

The global structure and time evolution of dayside magnetopause surface eigenmodes

Theoretical work and recent observations suggest that the dayside magnetopause may support its own eigenmode, consisting of propagating surface waves which reflect at the northern and southern ionospheres. These magnetopause surface eigenmodes (MSEs) are a potential source of magnetospheric ultralow‐frequency (ULF) waves with frequencies less than 2 mHz. Here we use the Space Weather Modeling Framework to study the magnetospheric response to impulsive solar wind dynamic pressure increases. Waves with 1.8 mHz frequency are excited whose global properties are largely consistent with theoretical predictions for MSE and cannot be explained by other known ULF wave modes. These simulation results lead to two key findings: (1) MSE can be sustained in realistic magnetic field geometries with nonzero flow shear and finite current layer thickness at the magnetopause and (2) MSE can seed the growth of tailward propagating surface waves via the Kelvin‐Helmholtz instability.Key PointsDayside ULF response to pulse consistent with magnetopause surface eigenmodeMagnetopause surface eigenmodes are a potential source of ULF waves below 2 mHzMagnetopause surface eigenmodes seed tailward propagating surface wave growthPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/111803/1/grl52799.pd

Intensity oscillations in the carbon 1s ionization cross sections of 2-butyne

Carbon 1s photoelectron spectra for 2-butyne (CH3C CCH3) measured in the photon energy range from threshold to 150 eV above threshold show oscillations in the intensity ratio C2,3/C1,4. Similar oscillations have been seen in chloroethanes, where the effect has been attributed to EXAFS-type scattering from the substituent chlorine atoms. In 2-butyne, however, there is no high-Z atom to provide a scattering center and, hence, oscillations of the magnitude observed are surprising. The results have been analyzed in terms of two different theoretical models: a density-functional model with B-spline atom-centered functions to represent the continuum electrons and a multiple-scattering model using muffin-tin potentials to represent the scattering centers. Both methods give a reasonable description of the energy dependence of the intensity ratios. (C) 2013 AIP Publishing LLC.Copyright 2013 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. This is the publisher’s final pdf. The published article is copyrighted by American Physical Society and can be found at: http://www.aps.org/.Keywords: Photoelectron, Energies, Absorption fine structure, PhotoionizationKeywords: Photoelectron, Energies, Absorption fine structure, Photoionizatio