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

Smoothed Particle Hydrodynamics and Magnetohydrodynamics

This paper presents an overview and introduction to Smoothed Particle Hydrodynamics and Magnetohydrodynamics in theory and in practice. Firstly, we give a basic grounding in the fundamentals of SPH, showing how the equations of motion and energy can be self-consistently derived from the density estimate. We then show how to interpret these equations using the basic SPH interpolation formulae and highlight the subtle difference in approach between SPH and other particle methods. In doing so, we also critique several `urban myths' regarding SPH, in particular the idea that one can simply increase the `neighbour number' more slowly than the total number of particles in order to obtain convergence. We also discuss the origin of numerical instabilities such as the pairing and tensile instabilities. Finally, we give practical advice on how to resolve three of the main issues with SPMHD: removing the tensile instability, formulating dissipative terms for MHD shocks and enforcing the divergence constraint on the particles, and we give the current status of developments in this area. Accompanying the paper is the first public release of the NDSPMHD SPH code, a 1, 2 and 3 dimensional code designed as a testbed for SPH/SPMHD algorithms that can be used to test many of the ideas and used to run all of the numerical examples contained in the paper.Comment: 44 pages, 14 figures, accepted to special edition of J. Comp. Phys. on "Computational Plasma Physics". The ndspmhd code is available for download from http://users.monash.edu.au/~dprice/ndspmhd

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

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

Cluster Magnetic Fields from Galactic Outflows

We performed cosmological, magneto-hydrodynamical simulations to follow the evolution of magnetic fields in galaxy clusters, exploring the possibility that the origin of the magnetic seed fields are galactic outflows during the star-burst phase of galactic evolution. To do this we coupled a semi-analytical model for magnetized galactic winds as suggested by \citet{2006MNRAS.370..319B} to our cosmological simulation. We find that the strength and structure of magnetic fields observed in galaxy clusters are well reproduced for a wide range of model parameters for the magnetized, galactic winds and do only weakly depend on the exact magnetic structure within the assumed galactic outflows. Although the evolution of a primordial magnetic seed field shows no significant differences to that of galaxy clusters fields from previous studies, we find that the magnetic field pollution in the diffuse medium within filaments is below the level predicted by scenarios with pure primordial magnetic seed field. We therefore conclude that magnetized galactic outflows and their subsequent evolution within the intra-cluster medium can fully account for the observed magnetic fields in galaxy clusters. Our findings also suggest that measuring cosmological magnetic fields in low-density environments such as filaments is much more useful than observing cluster magnetic fields to infer their possible origin.Comment: Minor revision for publication in MNRA

Cosmological Simulations using GCMHD+

Radio observations of galaxy clusters show that the intra cluster medium is permeated by \mu G magnetic fields. The origin and evolution of these cosmological magnetic fields is currently not well understood and so their impact on the dynamics of structure formation is not known. Numerical simulations are required to gain a greater understanding and produce predictions for the next generation of radio telescopes. We present the galactic chemodynamics smoothed particle magnetohydrodynamic (SPMHD) code (GCMHD+), which is an MHD implementation for the cosmological smoothed particle hydrodynamic code GCD+. The results of 1, 2 and 3 dimensional tests are presented and the performance of the code is shown relative to the ATHENA grid code. GCMHD+ shows good agreement with the reference solutions produced by ATHENA. The code is then used to simulate the formation of a galaxy cluster with a simple primordial magnetic field embedded in the gas. A homogeneous seed field of 10^-11 G is amplified by a factor of 10^3 during the formation of the cluster. The results show good agreement with the profiles found in other magnetic cluster simulations of similar resolution.Comment: 20 pages, 31 figures, accepted for publication in MNRA