Correlated electron-ion dynamics: the excitation of atomic motion by energetic electrons

Correlated electron-ion dynamics (CEID) is an extension of molecular dynamics that allows us to introduce in a correct manner the exchange of energy between electrons and ions. The formalism is based on a systematic approximation: small amplitude moment expansion. This formalism is extended here to include the explicit quantum spread of the ions and a generalization of the Hartree-Fock approximation for incoherent sums of Slater determinants. We demonstrate that the resultant dynamical equations reproduce analytically the selection rules for inelastic electron-phonon scattering from perturbation theory, which control the mutually driven excitations of the two interacting subsystems. We then use CEID to make direct numerical simulations of inelastic current-voltage spectroscopy in atomic wires, and to exhibit the crossover from ionic cooling to heating as a function of the relative degree of excitation of the electronic and ionic subsystems.

Energetic costs of parasitism in the Cape ground squirrel Xerus inauris

Parasites have been suggested to influence many aspects of host behaviour. Some of these effects may be mediated via their impact on host energy budgets. This impact may include effects on both energy intake and absorption as well as components of expenditure, including resting metabolic rate (RMR) and activity (e.g. grooming). Despite their potential importance, the energy costs of parasitism have seldom been directly quantified in a field setting. Here we pharmacologically treated female Cape ground squirrels (Xerus inauris) with anti-parasite drugs and measured the change in body composition, the daily energy expenditure (DEE) using doubly labelled water, the RMR by respirometry and the proportions of time spent looking for food, feeding, moving and grooming. Post-treatment animals gained an average 19 g of fat or approximately 25 kJ d(-1). DEE averaged 382 kJ d-1 prior to and 375 kJ d-1 post treatment (p> 0.05). RMR averaged 174 kJ d-1 prior to and 217 kJ d-1 post treatment (p

Strategies toward the design of energetic ionic liquids: nitro- and nitrile-substituted N,N '-dialkylimidazolium salts

Twelve novel 1,3-dialkylimidazolium salts containing strongly electron-withdrawing nitro-and cyano-functionalities directly appended to the cationic heterocyclic rings have been synthesized; the influences of the substituents on both formation and thermal properties of the resultant ionic liquids have been determined by DSC, TGA, and single crystal X-ray diffraction, showing that an electron-withdrawing nitro-substituent can be successfully appended and has a similar influence on the melting behaviour as that of corresponding methyl group substitution. Synthesis of di-, or trinitro-substituted 1,3-dialkylimidazolium cations was unsuccessful due to the resistance of dinitro-substituted imidazoles to undergo either N-alkylation or protonation, while 1-alkyl- 4,5-dicyanoimidazoles were successfully alkylated to obtain 1,3-dialkyl-4,5-dicyanoimidazolium salts. Five crystal structures ( one of each cation type) show that, in the solid state, the NO2-group has little significant effect, beyond the steric contribution, on the crystal packing.

Prediction of the formation and stabilities of energetic salts and ionic liquids based on ab initio electronic structure calculations

A computational approach to predict the thermodynamics for forming a variety of imidazolium-based salts and ionic liquids from typical starting materials is described. The gas-phase proton and methyl cation acidities of several protonating and methylating agents, as well as the proton and methyl cation affinities of many important methyl-, nitro-, and cyano- substituted imidazoles, have been calculated reliably by using the computationally feasible DFT (B3LYP) and MP2 (extrapolated to the complete basis set limit) methods. These accurately calculated proton and methyl cation affinities of neutrals and anions are used in conjunction with an empirical approach based on molecular volumes to estimate the lattice enthalpies and entropies of ionic liquids, organic solids, and organic liquids. These quantities were used to construct a thermodynamic cycle for salt formation to reliably predict the ability to synthesize a variety of salts including ones with potentially high energetic densities. An adjustment of the gas phase thermodynamic cycle to account for solid- and liquid-phase chemistries provides the best overall assessment of salt formation and stability. This has been applied to imidazoles (the cation to be formed) with alkyl, nitro, and cyano substituents. The proton and methyl cation donors studied were as follows: HCl, HBr, HI, (HO)(2)SO2, HSO3CF3 (TfOH), and HSO3(C6H4)CH3 (TsOH); CH3Cl, CH3Br, CH3I, (CH3O)(2)SO2, CH3SO3CF3 (TfOCH3) and CH3SO3(C6H4)CH3 (TsOCH3). As substitution of the cation with electron-withdrawing groups increases, the triflate reagents appear to be the best overall choice as protonating and methylating agents. Even stronger alkylating agents should be considered to enhance the chances of synthetic success. When using the enthalpies of reaction for the gas-phase reactants (eq 6) to form a salt, a cutoff value of - 13 kcal mol(-1) or lower (more negative) should be used as the minimum value for predicting whether a salt can be synthesized.

1-butyl-3-methylimidazolium 3,5-dinitro-1,2,4-triazolate: a novel ionic liquid containing a rigid, planar energetic anion

The novel ionic liquid, 1-butyl-3-methylimidazolium 3,5-dinitro-1,2,4-triazolate has been synthesized and exhibits an unexpectedly low melting point (35 degreesC) considering the size and shape of the rigid, planar anion; analogous tetraalkylammonium salts (methyl, ethyl and n-butyl) have also been prepared and the tetraethylammonium example was characterized by single crystal X-ray diffraction.

Measurements of energetic proton transport through magnetized plasma from intense laser interactions with solids

Protons with energies up to 18 MeV have been measured from high density laser-plasma interactions at incident laser intensities of 5 X 10(19) W/cm(2). Up to 10(12) protons with energies greater than 2 MeV were observed to propagate through a 125 mu m thick aluminum target and measurements of their angular deflection were made. It is likely that the protons originate from the front surface of the target and are bent by large magnetic fields which exist in the target interior. To agree with our measurements these fields would be in excess of 30 MG and would be generated by the beam of fast electrons which is also observed.

Production of radioactive nuclides by energetic protons generated from intense laser-plasma interactions

Nuclear activation has been observed in materials exposed to the ablated plasma generated from high intensity laser-solid interactions (at focused intensities up to 2x10(19) W/cm(2)) and is produced by protons having energies up to 30 MeV. The energy spectrum of the protons is determined from these activation measurements and is found to be consistent with other ion diagnostics. The possible development of this technique for

Mono-energetic ion beam acceleration in solitary waves during relativistic transparency using high-contrast circularly polarized short-pulse laser and nanoscale targets

In recent experiments at the Trident laser facility, quasi-monoenergetic ion beams have been obtained from the interaction of an ultraintense, circularly polarized laser with a diamond-like carbon target of nm-scale thickness under conditions of ultrahigh laser pulse contrast. Kinetic simulations of this experiment under realistic laser and plasma conditions show that relativistic transparency occurs before significant radiation pressure acceleration and that the main ion acceleration occurs after the onset of relativistic transparency. Associated with this transition are a period of intense ion acceleration and the generation of a new class of ion solitons that naturally give rise to quasi-monoenergetic ion beams. An analytic theory has been derived for the properties of these solitons that reproduces the behavior observed in kinetic simulations and the experiments. © 2011 American Institute of Physics.

Environmental Challenges and Physiological Solutions: Comparative Energetic Daily Rhythms of Field Mice Populations from Different Ecosystems

Daily and seasonal variations in physiological characteristics of mammals can be considered adaptations to temporal habitat variables. Across different ecosystems, physiological adjustments are expected to be sensitive to different environmental signals such as changes in photoperiod, temperature or water and food availability; the relative importance of a particular signal being dependent on the ecosystem in question. Energy intake, oxygen consumption (VO) and body temperature (T) daily rhythms were compared between two populations of the broad-toothed field mouse Apodemus mystacinus, one from a Mediterranean and another from a sub-Alpine ecosystem. Mice were acclimated to short-day (SD) 'winter' and long-day (LD) 'summer' photoperiods under different levels of salinity simulating osmotic challenges. Mediterranean mice had higher VO values than sub-Alpine mice. In addition, mice exposed to short days had higher VO values when given water with a high salinity compared with mice exposed to long days. By comparison, across both populations, increasing salinity resulted in a decreased T in SD- but not in LD-mice. Thus, SD-mice may conserve energy by decreasing T during ('winter') conditions which are expected to be cool, whereas LD-mice might do the opposite and maintain a higher T during ('summer') conditions which are expected to be warm. LD-mice behaved to reduce energy expenditure, which might be considered a useful trait during 'summer' conditions. Overall, increasing salinity was a clear signal for Mediterranean-mice with resultant effects on VO and T daily rhythms but had less of an effect on sub-Alpine mice, which were more responsive to changes in photoperiod. Results provide an insight into how different populations respond physiologically to various environmental challenges.