The addition of CO2 to four superbase ionic liquids: a DFT study

The addition of carbon dioxide to four superbase ionic liquids, [P3333][Benzim], [P3333][124Triz], [P3333][123Triz] and [P3333][Bentriz] was studied using a molecular DFT approach involving anions alone and individual ion pairs. Intermolecular bonding within the individual ion pairs is characterised by a number of weak hydrogen bonds, with the superbase anion geometrically arranged so as to maximize interactions between the heterocyclic N atoms and the cation. The pairing energies show no correlation to the observed CO2 adsorption capacity. Addition of CO2 to the anion alone clearly resulted in the formation of a covalently-bound carbamate function with the strength of binding correlated to experimental capacity. In the ion pair however the cation significantly alters the nature of the bonding such that the overall cohesive energy is reduced. Formation of a strong carbamate function occurs at the expense of weakening the interaction between anion and cation. In the more weakly absorbing ion pairs which contain [123Triz]- and [Bentriz]-, the carbamate-functionalised systems are very close in energy to adducts in which CO2 is more weakly bound, suggesting an equilibrium between the chemi- and physisorbed CO2.

Strong second harmonic generation in SiC, ZnO, GaN two-dimensional hexagonal crystals from first-principles many-body calculations

The second harmonic generation (SHG) intensity spectrum of SiC, ZnO, GaN two-dimensional hexagonal crystals is calculated by using a real-time first-principles approach based on Green's function theory [Attaccalite et al., Phys. Rev. B: Condens. Matter Mater. Phys. 2013 88, 235113]. This approach allows one to go beyond the independent particle description used in standard first-principles nonlinear optics calculations by including quasiparticle corrections (by means of the GW approximation), crystal local field effects and excitonic effects. Our results show that the SHG spectra obtained using the latter approach differ significantly from their independent particle counterparts. In particular they show strong excitonic resonances at which the SHG intensity is about two times stronger than within the independent particle approximation. All the systems studied (whose stabilities have been predicted theoretically) are transparent and at the same time exhibit a remarkable SHG intensity in the range of frequencies at which Ti:sapphire and Nd:YAG lasers operate; thus they can be of interest for nanoscale nonlinear frequency conversion devices. Specifically the SHG intensity at 800 nm (1.55 eV) ranges from about 40-80 pm V(-1) in ZnO and GaN to 0.6 nm V(-1) in SiC. The latter value in particular is 1 order of magnitude larger than values in standard nonlinear crystals.

Cement As a Waste Form for Nuclear Fission Products: The Case of 90Sr and Its Daughters

One of the main challenges faced by the nuclear industry is the long-term confinement of nuclear waste. Because it is inexpensive and easy to manufacture, cement is the material of choice to store large volumes of radioactive materials, in particular the low-level medium-lived fission products. It is therefore of utmost importance to assess the chemical and structural stability of cement containing radioactive species. Here, we use ab initio calculations based on density functional theory (DFT) to study the effects of ⁹⁰Sr insertion and decay in C-S-H (calcium-silicate-hydrate) in order to test the ability of cement to trap and hold this radioactive fission product and to investigate the consequences of its β-decay on the cement paste structure. We show that ⁹⁰Sr is stable when it substitutes the Ca²⁺ ions in C-S-H, and so is its daughter nucleus ⁹⁰Y after β-decay. Interestingly, ⁹⁰Zr, daughter of ⁹⁰Y and final product in the decay sequence, is found to be unstable compared to the bulk phase of the element at zero K but stable when compared to the solvated ion in water. Therefore, cement appears as a suitable waste form for ⁹⁰Sr storage.

Engineering Simulations

Over recent years, ionic liquids have emerged as a class of novel fluids that have inspired the development of a number of new products and processes. The ability to design these materials with specific functionalities and properties means that they are highly relevant to the growing philosophy of chemical-product design. This is particularly appropriate in the context of a chemical industry that is becoming increasingly focussed on small-volume, high-value added products with relatively short times to market. To support such product and process development, a number of tools can be utilised. A key requirement is that the tool can predict the physical properties and activity coefficients of multi-component mixtures and, if required, model the process in which the materials will be used. Multi-scale simulations that span density functional theory (DFT) to process-engineering computations can address the relevant time and length scales and have increased in usage with the availability of cheap and powerful computers. Herein we will discuss the area of engineering calculations relating to the design of ionic liquid processes, that is, the computational tools that bridge this gap and allow for process simulation tools to utilise and assist in the design of ionic liquids. It will be shown that, at present, it is possible to use available tools to estimate many important properties of ionic liquids and mixtures containing them with a sufficient level of accuracy for preliminary design and selection.

Volumetric Carbon Content Calculations: A Geostatistical and Compositional Approach

This study applies spatial statistical techniques including cokriging to integrate airborne geophysical (radiometric) data with ground-based measurements of peat depth and soil organic carbon (SOC) to monitor change in peat cover for carbon stock calculations. The research is part of the EU funded Tellus Border project and is supported by the INTERREG IVA development programme of the European Regional Development Fund, which is managed by the Special EU Programmes Body (SEUPB). The premise is that saturated peat attenuates the radiometric signal from underlying soils and rocks. Contemporaneous ground-based measurements were collected to corroborate mapped estimates and develop a statistical model for volumetric carbon content (VCC) to 0.5 metres. Field measurements included ground penetrating radar, gamma ray spectrometry and a soil sampling methodology which measured bulk density and soil moisture to determine VCC. One aim of the study was to explore whether airborne radiometric survey data can be used to establish VCC across a region. To account for the footprint of airborne radiometric data, five cores were obtained at each soil sampling location: one at the centre of the ground radiometric equivalent sample location and one at each of the four corners 20 metres apart. This soil sampling strategy replicated the methodology deployed for the Tellus Border geochemistry survey. Two key issues will be discussed from this work. The first addresses the integration of different sampling supports for airborne and ground measured data and the second discusses the compositional nature of the VOC data.

Towards a spectroscopically accurate set of potentials for heavy hydride laser cooling candidates: effective core potential calculations of BaH

BaH (and its isotopomers) is an attractive molecular candidate for laser cooling to ultracold temperatures and a potential precursor for the production of ultracold gases of hydrogen and deuterium. The theoretical challenge is to simulate the laser cooling cycle as reliably as possible and this paper addresses the generation of a highly accurate ab initio $^{2}\Sigma^+$ potential for such studies. The performance of various basis sets within the multi-reference configuration-interaction (MRCI) approximation with the Davidson correction (MRCI+Q)is tested and taken to the Complete Basis Set (CBS) limit. It is shown that the calculated molecular constants using a 46 electron Effective Core-Potential (ECP) and even-tempered augmented polarized core-valence basis sets (aug-pCV$n$Z-PP, n= 4 and 5) but only including three active electrons in the MRCI calculation are in excellent agreement with the available experimental values. The predicted dissociation energy De for the X$^2\Sigma^+$ state (extrapolated to the CBS limit) is 16895.12 cm$^{-1}$ (2.094 eV), which agrees within 0.1$\%$ of a revised experimental value of <16910.6 cm$^{-1}$, while the calculated re is within 0.03 pm of the experimental result.

Relativistic radiatively damped R -matrix calculations of the electron-impact excitation of helium-like iron and krypton

Electron-impact excitation data for He-like ions are of significant importance for diagnostic applications to both laboratory and astrophysical plasmas. Here we report on the first fully relativistic R -matrix calculations with radiation damping for the He-like ions Fe 24+ and Kr 34+ . Effective collision strengths for these two ions have been determined with and without damping over a wide temperature range for all transitions between the 49 levels through n = 5. We find that damping has a pronounced effect on the effective collision strengths for excitation to some of the low-lying levels, but its effect on excitation to the vast majority of levels is small. At the energy of a resonance peak, we also investigate the effect of radiation damping on the angular distribution of scattered electrons. Finally, we compare our results for Fe 24+ with an earlier intermediate coupling frame transformation R -matrix calculation with radiation damping by Whiteford et al ( J. Phys. B: At. Mol. Opt. Phys. 34 3179) and find good agreement, especially for excitation to the lower levels.

Intermediate-coupling R -matrix calculations of electron-impact excitation of Fe 5+

For applications to laboratory and astrophysical plasmas, there is a great need for accurate electron-impact excitation data between individual levels in the lower charge-state ions of iron. Recently, we have reported on the first intermediate-coupling R -matrix calculation of electron-impact excitation in Fe 4+ , in which the close-coupling expansion of the target included levels from both ground and excited configurations (Ballance et al 2007 J. Phys. B: At. Mol. Opt. Phys. [/0953-4075/40/23/f01] 40 F327 , 2008 Europhys. News 39 14). In this paper, we present the results of two large intermediate-coupling Dirac R -matrix calculations of electron-impact excitation of Fe 5+ . The results from the two calculations, which differ only in the configuration–interaction expansions of the target, are compared. These comparisons provide some indication of the accuracy of the calculations and the resulting data should be useful in modelling plasmas containing iron.

Electron-impact excitation of Fe2: a comparison of intermediate coupling frame transformation, Breit-Pauli and Dirac R-matrix calculations

Modeling the spectral emission of low-charge iron group ions enables the diagnostic determination of the local physical conditions of many cool plasma environments such as those found in H II regions, planetary nebulae, active galactic nuclei etc. Electron-impact excitation drives the population of the emitting levels and, hence, their emissivities. By carrying-out Breit-Pauli and intermediate coupling frame transformation (ICFT) R-matrix calculations for the electron-impact excitation of Fe$^{2+}$ which both use the exact same atomic structure and the same close-coupling expansion, we demonstrate the validity of the application of the powerful ICFT method to low-charge iron group ions. This is in contradiction to the finding of Bautista et al. [Ap.J.Lett, 718, L189, (2010)] who carried-out ICFT and Dirac R-matrix calculations for the same ion. We discuss possible reasons.

Photoionization cross section calculations for the halogen-like ions Kr + and Xe +

Photoionization cross section calculations on the halogen-like ions; Kr + and Xe + have been performed for a photon energy range from each ion threshold to 15 eV, using large-scale close-coupling calculations within the Dirac--Coulomb R -matrix approximation. The results from our theoretical work are compared with recent measurements made at the ASTRID merged-beam set-up at the University of Aarhus in Denmark and from the Fourier transform ion cyclotron resonance trap method at the SOLEIL synchrotron radiation facility in Saint-Aubin, France Bizau et al (2011 J. Phys. B: At. Mol. Opt. Phys. 44 055205) and the advanced light source M{ü}ller (2012 private communication), Aguliar et al (2012 J. Phys.: Conf. Ser . at press). For each of these complex ions our theoretical cross section results over the photon energy range investigated are seen to be in excellent agreement with experiment. Resonance energy positions and quantum defects of the prominent Rydberg resonances series identified in the spectra are compared with experiment for these complex halogen-like ions.

PAMOP: Petascale atomic, molecular and optical collision calculations

Petaflop architectures are currently being utilized efficiently to perform large scale computations in Atomic, Molecular and Optical Collisions. We solve the Schr\"odinger or Dirac equation for the appropriate collision problem using the R-matrix or R-matrix with pseudo-states approach. We briefly outline the parallel methodology used and implemented for the current suite of Breit-Pauli and DARC codes. In this report, various examples are shown from our theoretical results compared with experimental results obtained from Synchrotron Radiation facilities where the Cray architecture at HLRS is playing an integral part in our computational projects.

Dirac R -matrix calculations of electron-impact excitation of neon-like krypton

We have employed the Dirac R -matrix method to determine electron-impact excitation cross sections and effective collision strengths in Ne-like Kr 26+ . Both the configuration-interaction expansion of the target and the close-coupling expansion employed in the scattering calculation included 139 levels up through n = 5. Many of the cross sections are found to exhibit very strong resonances, yet the effects of radiation damping on the resonance contributions are relatively small. Using these collisional data along with multi-configuration Dirac–Fock radiative rates, we have performed collisional-radiative modeling calculations to determine line-intensity ratios for various radiative transitions that have been employed for diagnostics of other Ne-like ions.

Collisional-radiative calculations of He line emission in low-temperature plasmas

We present spectral modeling results for neutral helium. Our underlying atomic data contains radiative transition rates that are generated from atomic structure calculations and electron-impact excitation rates, that are determined from both the standard R-matrix method and the R-matrix with pseudostates RMPS method. In this paper, we focus on transitions of particular importance to diagnostic line ratios. For example, our calculated rate coefficient for the electron-impact transition 1s3s 1S→1s3p 1P, which has a pronounced effect on the 728.1 nm diagnostic spectral line, is found to be in good agreement with previous experimental mea- surements. We also consider transitions from the 1s2 1S ground and 1s2s 3S terms to terms of the n=4 shell. They are found to be affected significantly by coupling of the bound states to the target continuum continuum coupling, which is included in our RMPS calculation, but not in our standard R-matrix calculation. We perform collisional-radiative calculations to determine spectral line intensity ratios for three ratios of particular interest, namely the 504.8 nm/471.3 nm, 492.2 nm/471.3 nm, and 492.2 nm/504.8 nm line ratios. Comparing our results determined from the RMPS excitation rates with those from the standard R-matrix excitation rates, we find that continuum coupling affects the rate coefficients significantly, leading to different values for all three line ratios. We also compare our modeling results with spectral measurements taken recently on the Auburn Helicon plasma device, finding that the ground and metastable populations are not in equilibrium, and that the experimental measurements are more consistent with the 1s2s 3S metastable term populations being short lived in the plasma.