Glucose solvation by the ionic liquid 1,3-dimethylimidazolium chloride: A simulation study

Simulations of beta-glucose in the ionic liquid 1,3-dimethylimidazoliurn chloride have been performed in order to examine the solvation environment of the carbohydrate. Both single molecule and 1:5 glucose:ionic liquid (16.7 wt %) solutions are Studied, and the hydrogen bonding between sugar and solvent is examined. The primary solvation shell around the perimeter of the glucose ring consists predominantly of chloride anions which hydrogen bond to the hydroxyl groups. A small presence of the cation is also found, with the association Occurring through the weakly acidic hydrogen at the 2-position of the imidazolium ring interacting with the oxygen atoms of the sugar secondary hydroxyls. An average chloride coordination number of 4 is found around the glucose for both the single molecule and high concentration Simulations, despite the reduced chloride:glucose ratio in the latter case. In relation to the cation, the glucose molecules occupy positions above and below the plane of the imidazolium ring. Importantly, even at high glucose concentrations, no significant change in the anion-cation interactions and overall liquid structure of the ionic liquid is found, indicating that the glucose is readily accommodated by the solvent at this concentration. Dominant contributions to the sugar-ionic liquid interaction energy come from favorable hydrogen bonding (electrostatic) interactions between hydroxyls and chlorides, although a small favorable van der Waals energy contribution is also seen between the sugar and cations suggesting that the cation could be tailored in order to further improve the dissolution of glucose/cellulose in ionic liquid systems.

A density functional theory study of the a-olefin selectivity in Fischer-Tropsch synthesis

We studied the alpha-olefin selectivity in Fischer-Tropsch (FT) synthesis using density functional theory (131717) calculations. We calculated the relevant elementary steps from C-2 to C-6 species. Our results showed that the barriers of hydrogenation and dehydrogenation reactions were constant with different chain lengths, and the chemisorption energies of alpha-olefins from DFT calculations also were very similar, except for C-2 species. A simple expression of the paraffin/olefin ratio was obtained based on a kinetic model. Combining the expression of the paraffin/olefin ratio and our calculation results, experimental findings are satisfactorily explained. We found that the physical origin of the chain length dependence of paraffin/olefin ratio is the chain length dependence of both the van der Waals interaction between adsorbed alpha-olefins and metal surfaces and the entropy difference between adsorbed and gaseous alpha-olefins, and that the greater chemisorption energy of ethylene is the main reason for the abnormal ethane/ethylene ratio. (c) 2008 Elsevier Inc. All rights reserved.

Ultrafast Laser-Driven Excitation Dynamics in Ne: An Ab Initio Time-Dependent R-Matrix Approach

An attosecond pump-probe scheme that combines the use of a free-electron laser pulse with an ultrashort pulse is applied in order to explore the ultrafast excitation dynamics in Ne. We describe the multielectron dynamics using a new nonperturbative time-dependent R-matrix theory. This theory enables the interaction of ultrashort light fields with multielectron atoms and atomic ions to be determined from first principles. By probing the emission of an inner 2s electron from Ne we are also able to study the bound state population dynamics during the free-electron laser pulse.

The component masses of the cataclysmic variable V347 Puppis

We present time-resolved spectroscopy and photometry of the double-lined eclipsing cataclysmic variable V347 Pup ( = LB 1800). There is evidence of irradiation on the inner hemisphere of the secondary star, which we correct for using a model to give a secondary-star radial velocity of K R = 198 +/- 5 km s(-1). The rotational velocity of the secondary star in V347 Pup is found to be v sin i = 131 +/- 5 km s(-1) and the system inclination is i = 84degrees.0 +/- 2degrees.3. From these parameters we obtain masses of M-1 = 0.63 +/- 0.04 M for the white dwarf primary and M-2 = 0.52 +/- 0.06 M for the M0.5V secondary star, giving a mass ratio of q = 0.83 +/- 0.05. On the basis of the component masses, and the spectral type and radius of the secondary star in V347 Pup, we find tentative evidence for an evolved companion. V347 Pup shows many of the characteristics of the SW Sex stars, exhibiting single-peaked emission lines, high-velocity S-wave components and phase-offsets in the radial velocity curve. We find spiral arms in the accretion disc of V347 Pup and measure the disc radius to be close to the maximum allowed in a pressureless disc.

Time-dependent R -matrix theory for ultrafast atomic processes

We describe an ab initio nonperturbative time-dependent R-matrix theory for ultrafast atomic processes. This theory enables investigations of the interaction of few-femtosecond and -attosecond pulse lasers with complex multielectron atoms and atomic ions. A derivation and analysis of the basic equations are given, which propagate the atomic wave function in the presence of the laser field forward in time in the internal and external R-matrix regions. To verify the accuracy of the approach, we investigate two-photon ionization of Ne irradiated by an intense laser pulse and compare current results with those obtained using the R-matrix Floquet method and an alternative time-dependent method. We also verify the capability of the current approach by applying it to the study of two-dimensional momentum distributions of electrons ejected from Ne due to irradiation by a sequence of 2 as light pulses in the presence of a 780 nm laser field.

Ultrafast Probing of Collective Electron Dynamics Driven by Dielectronic Repulsion

We use the time-dependent R-matrix approach to investigate an ultrashort pump-probe scheme to observe collective electron dynamics in C(+). The ionization probability of a coherent superposition of the 2s2p(2) (2)D and (2)S states shows rapid modulation due to collective dynamics of the two equivalent 2p electrons, with the modulation frequency linked to the dielectronic repulsion. The best insight into this collective dynamics is achieved by a transformation from LS symmetry to the uncoupled basis. Such dynamics may be important in high-harmonic generation using open-shell atoms and ions.

Dynamic resonances and tunnelling in the multiphoton ionization of argon

We present results of wavepacket simulations for multiphoton ionization in argon. A single active electron model is applied to estimate the single-electron ionization rates and photoelectron energy distributions for lambda = 390 nm light with intensities up to I = 2 x 10(14) W cm(-2). The multiphoton ionization rates are compared with R-matrix Floquet calculations and found to be in very good agreement. The photoelectron energy distribution is used to study the nature of ionization at the higher intensities. Our results are consistent with recent calculations and experiments which show the imprint of the tunnelling process in the multiphoton regime. For few-cycle intense pulses, we find that the strong modulation of intensity and increased bandwidth leads to dynamic mixing of the 3d and 5s resonances.

Crystal structures of imidazolium bis(trifluoromethanesulfonyl)imide 'ionic liquid' salts: the first organic salt with a cis-TFSI anion conformation

Crystal structures of two examples of an important class of ionic liquids, 1,3-dimethylimidazolium and 1,2,3-triethylimidazolium bis(trifluoromethanesulfonyl)imide have been characterized by single crystal X-ray diffraction. The anion in the 1,3-dimethylimidazolium example (mp 22 degreesC), adopts an unusual cis-geometry constrained by bifurcated cation-anion C-H...O hydrogen-bonds from the imidazolium cation to the anion resulting in the formation of fluorous layers within the solid-state structure. In contrast, in the 1,2,3-triethylimidazolium salt (mp 57 degreesC), the ions are discretely packed with only weak C-H...O contacts between the ions close to the van der Waals separation distances, and with the anion adopting the twisted conformation observed for all other examples from the limited set of organic bis( trifluoromethanesulfonyl) imide crystal structures. The structures are discussed in terms of the favorable physical properties that bis(trifluoromethanesulfonyl) imide anions impart in ionic liquids.

High precision C-14 dating of Holocene peat deposits: A comparison of Bayesian calibration and wiggle-matching approaches

The chronologies of five northern European ombrotrophic peat bogs subjected to a large ANIS C-14 dating effort (32-44 dates/site) are presented here. The results of Bayesian calibration (BCal) of dates with a prior assumption of chronological ordering were compared with a Bayesian wiggle-match approach (Bpeat) which assumes constant linear accumulation over sections of the peat profile. Interpolation of BCal age estimates of dense sequences of C-14 dates showed variable patterns of peat accumulation with time, with changes in accumulation occurring at intervals ranging from 20 to 50 cm. Within these intervals, peat accumulation appeared to be relatively linear. Close analysis suggests that some of the inferred variations in accumulation rate were related to the plant macrofossil composition of the peat. The wiggle-matched age-depth models had relatively high chronological uncertainty within intervals of closely spaced 14 C dates, suggesting that the premise of constant linear accumulation over large sections of the peat profile is unrealistic. Age models based on the assumption of linear accumulation over large parts of a peat core (and therefore only effective over millennial timescales), are not compatible with studies examining environmental change during the Holocene, where variability often occurs at decadal to centennial time-scales. Ideally, future wiggle-match age models should be constrained, with boundaries between sections based on the plant macrofossil composition of the peat and physical-chemical parameters such as the degree of decomposition. Strategies for the selection of material for dating should be designed so that there should be enough C-14 dates to accurately reconstruct the peat accumulation rate of each homogeneous stratigraphic unit. (c) 2006 Elsevier Ltd. All rights reserved.

Carbon leakage revisited: unilateral climate policy with directed technical change

Using a stylized theoretical model, we argue that current economic analyses of climate policy tend to over-estimate the degree of carbon leakage, as they abstract from the effects of induced technological change. We analyse carbon leakage in a two-country model with directed technical change, where only one of the countries enforces an exogenous cap on emissions. Climate policy induces changes in relative prices, that cause carbon leakage through a terms-of-trade effect. However, these changes in relative prices also affect the incentives to innovate in different sectors. This leads to a counterbalancing induced-technology effect, which always reduces carbon leakage. We therefore conclude that the leakage rates reported in the literature may be too high, as these estimates neglect the effect of price changes on the incentives to innovate.

IntCal09 and Marine09 radiocarbon age calibration curves, 0 - 50,000 years cal BP

The IntCal04 and Marine04 radiocarbon calibration curves have been updated from 12 cal kBP (cal kBP is here defined as thousands of calibrated years before AD 1950), and extended to 50 cal kBP, utilizing newly available data sets that meet the IntCal Working Group criteria for pristine corals and other carbonates and for quantification of uncertainty in both the ¹⁴C and calendar timescales as established in 2002. No change was made to the curves from 0-12 cal kBP. The curves were constructed using a Markov chain Monte Carlo (MCMC) implementation of the random walk model used for IntCal04 and Marine04. The new curves were ratified at the 20th International Radiocarbon Conference in June 2009 and are available in the Supplemental Material at www.radiocarbon.org.