We employ molecular dynamics (MD) simulation and experiment to investigate the structure, thermodynamics, and transport of N-methyl-N-butylpyrrolidinium bis(trifluoromethylsufonyl)imide ([pyr14][TFSI]), N-methyl-N-propylpyrrolidinium bis(fluorosufonyl)imide ([pyr13][FSI]), and 1-ethyl-3-methylimidazolium boron tetrafluoride ([EMIM][BF4]), as a function of Li-salt mole fraction (0.05 ≤ xLi(+) ≤ 0.33) and temperature (298 K ≤ T ≤ 393 K). Structurally, Li(+) is shown to be solvated by three anion neighbors in [pyr14][TFSI] and four anion neighbors in both [pyr13][FSI] and [EMIM][BF4], and at all levels of xLi(+) we find the presence of lithium aggregates. Pulsed field gradient spin-echo NMR measurements of diffusion and electrochemical impedance spectroscopy measurements of ionic conductivity are made for the neat ionic liquids as well as 0.5 molal solutions of Li-salt in the ionic liquids. Bulk ionic liquid properties (density, diffusion, viscosity, and ionic conductivity) are obtained with MD simulations and show excellent agreement with experiment. While the diffusion exhibits a systematic decrease with increasing xLi(+), the contribution of Li(+) to ionic conductivity increases until reaching a saturation doping level of xLi(+) = 0.10. Comparatively, the Li(+) conductivity of [pyr14][TFSI] is an order of magnitude lower than that of the other liquids, which range between 0.1 and 0.3 mS/cm. Our transport results also demonstrate the necessity of long MD simulation runs (∼200 ns) to converge transport properties at room temperature. The differences in Li(+) transport are reflected in the residence times of Li(+) with the anions (τ(Li/-)), which are revealed to be much larger for [pyr14][TFSI] (up to 100 ns at the highest doping levels) than in either [EMIM][BF4] or [pyr13][FSI]. Finally, to comment on the relative kinetics of Li(+) transport in each liquid, we find that while the net motion of Li(+) with its solvation shell (vehicular) significantly contributes to net diffusion in all liquids, the importance of transport through anion exchange increases at high xLi(+) and in liquids with large anions.

This paper presents a key to the larvae and pupae of 28 species of Culicoides found in Britain and to larvae and pupae of the genera Stilobezzia, Serromyia and Ceratopogon including the subgenera Ceratopogon and Isohelea. The keys are supplemented by descriptions of the larvae and pupae, including photographs of the fourth instars and figures of the so-called “hypopharynx” —the true epipharynx—of most of the larvae and by figures of specific characters of the pupae. Twenty-eight species of Culicoides larvae are described:—C. albicans, C. chiopterus, C. circumscriptus, C. cubitalis, C. cunctans, C. delta, C. fascipennis, C. grisescens, C. halophilus, C. heliophilus, C. impunctatus, C. lupicaris, C. maritimus, C. nubeculosus, C. obsoletus, C. odibilis, C. pcdlidicornis, C. pictipennis, C. pseudochiopterus, C. pulicaris, C. punctatus, C. riethi, C. salinarius, C. scoticus, C. simulator, C. stigma, C. truncorum, and C. vexans. The descriptions of the pupae include all the above, with the addition of C. parroti.An analysis has been made of the breeding preferences of Culicoides and it was found that species could be placed in one of six groups depending on the larval habitat. The six categories were:— (i) Bog, (ii) Fresh Water Marsh, (iii) Swamp, (iv) Mud, (v) Salt Water Marsh and (vi) Dung.The vertical distributions of seven species of Culicoides larvae are given. There are marked differences between the species in this respect.

This work is Part 1 in a two part series that investigates the interfacial decomposition chemistry of [pyr14][TFSI] and [EMIM][BF 4 ] ionic liquids (IL) at Li metal interfaces. Here, the decomposition is probed primarily through ab initio molecular dynamics (AIMD) simulations. For single ion pairs adsorbed on a Li(100) surface, hybrid ion states are found to emerge about the Fermi level. Interestingly, these states have a significant contribution from both ions, which suggests that the cathodic (reductive) stability could in part be governed by the anions. Room temperature AIMD simulations reveal rapid decomposition of the TFSI anion initiated by C−S and/or S−N bond cleavage due to charge transfer from Li to the anion. The unusual phenomenon of reductive decomposition of the anion is supported by recent experimental reports. The reaction products observed included LiF, LiO, Li 2 F, Li 2 O, SO 2 , NSO 2 , NSO 2 CF 3 , etc., which are all in excellent agreement with the XPS results. Initial decomposition reactions for both cations and the BF 4 anion were only observed in high temperature AIMD simulations. For bulk ILs interfaces with a Li(100) surface, interfacial decomposition reactions again result from charge transfer to the IL from the Li surface, in particular, to anions at the interfaces. The initial decomposition event at bulk interfaces is found to vary depending on the interface structure. The extensive computational analyses presented in this work provide valuable insights into the fundamental interfacial chemistry of ILs in contact with Li metal. In Part 2 1 of this series, we consider these results further by systematically examining ion reductive stability, the thermodynamics of decomposition, and kinetic limitations to decomposition using gas phase density functional theory (DFT) computations. Results from these studies can be used for further design of these, or perhaps other, ILs to obtain more stable solid electrolyte interface (SEI) layers to improve cycling in advanced battery chemistries.

Prey energy density values are crucial inputs to bioenergetic consumption models. Vertebrate predators in the northwest Atlantic consume a variety of prey species, but the proximate composition (PC; proportions of lipid, protein, ash and water) and energy density (ED; kJ g-l) of prey, and their variability, are known poorly. In this study, key prey species from Newfoundland and Labrador were studied: Atlantic cod Gadus morhua, American plaice Hippoglossoides platessoides, sand lance Ammodytes dubius, Arctic cod Boreogadus saida, northern shrimp Pandalus borealis, redfish Sebastes spp., Greenland halibut ReiDhardtius hippoglossoides, squid Illex lllecebrosus and Gonatus fabricji, capelin Mallotus villosus, Atlantic herring Clupea harengus and daubed shanny Lumpenus maculatus. PC and ED varied greatly among species and were influenced by size, season, geography and year. Herring, capelin and G. fabricii had the highest ED, whereas Atlantic cod, plaice, sand lance and shrimp had the lowest. Halibut and I. illecebrosusincreased in ED with size. EDs of capelin and redfish varied seasonally; that of plaice and sand lance did not, Herring and halibut had higher ED in the early 1990s than in recent years. Such variation in prey ED has important imphcations for digestive efficiency, foraging energetics, and dietary preferences of vertebrate predators.

We investigate how systematically increasing the accuracy of various molecular dynamics modeling techniques influences the structure and capacitance of ionic liquid electric double layers (EDLs). The techniques probed concern long-range electrostatic interactions, electrode charging (constant charge versus constant potential conditions), and electrolyte polarizability. Our simulations are performed on a quasi-two-dimensional, or slab-like, model capacitor, which is composed of a polarizable ionic liquid electrolyte, [EMIM][BF4], interfaced between two graphite electrodes. To ensure an accurate representation of EDL differential capacitance, we derive new fluctuation formulas that resolve the differential capacitance as a function of electrode charge or electrode potential. The magnitude of differential capacitance shows sensitivity to different long-range electrostatic summation techniques, while the shape of differential capacitance is affected by charging technique and the polarizability of the electrolyte. For long-range summation techniques, errors in magnitude can be mitigated by employing two-dimensional or corrected three dimensional electrostatic summations, which led to electric fields that conform to those of a classical electrostatic parallel plate capacitor. With respect to charging, the changes in shape are a result of ions in the Stern layer (i.e., ions at the electrode surface) having a higher electrostatic affinity to constant potential electrodes than to constant charge electrodes. For electrolyte polarizability, shape changes originate from induced dipoles that soften the interaction of Stern layer ions with the electrode. The softening is traced to ion correlations vertical to the electrode surface that induce dipoles that oppose double layer formation. In general, our analysis indicates an accuracy dependent differential capacitance profile that transitions from the characteristic camel shape with coarser representations to a more diffuse profile with finer representations.