Real single ion solvation free energies with quantum mechanical simulation

Single ion solvation free energies are one of the most important properties of electrolyte solutions and yet there is ongoing debate about what these values are. Only the values for neutral ion pairs are known. Here, we use DFT interaction potentials with molecular dynamics simulation (DFT-MD) combined with a modified version of the quasi-chemical theory (QCT) to calculate these energies for the lithium and fluoride ions. A method to correct for the error in the DFT functional is developed and very good agreement with the experimental value for the lithium fluoride pair is obtained. Moreover, this method partitions the energies into physically intuitive terms such as surface potential, cavity and charging energies which are amenable to descriptions with reduced models. Our research suggests that lithium's solvation free energy is dominated by the free energetics of a charged hard sphere, whereas fluoride exhibits significant quantum mechanical behavior that cannot be simply described with a reduced model.Comment: 13 pages, 4 figure

Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation (DFT-MD) and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry (CHA) for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.Comment: 28 pages, 5 figure

Structure and chemistry in the northwestern condensation of the Serpens molecular cloud core

We present single-dish and interferometric observations of gas and dust in the core of the Serpens molecular cloud, focusing on the northwestern condensation. Single-dish molecular line observations are used to probe the structure and chemistry of the condensation while high-resolution images of CS and CH_(3)0H are combined with continuum observations from λ = 1.3 mm to λ = 3.5 cm to study the subcondensations and overall distribution of dust. For the northwestern condensation, we derive a characteristic density of 3 x 10^5 cm^(-3) and an estimated total mass of approximately 70 M_⊙. We find compact molecular emission associated with the far-infrared source S68 FIRS 1, and with a newly detected subcondensation named S68 N. Comparison of the large-and small-scale emission reveals that most of the material in the northwest condensation is not directly associated with these compact sources, suggesting a youthful age for this region. CO J = 1 approaches 0 observations indicate widespread outflow activity. However, no unique association of embedded objects with outflows is possible with our observations. The SiO emission is found to be extended with the overall emission centered about S68 FIRS 1; the offset of the peak emission from all of the known continuum sources and the coincidence between the blueshifted SiO emission and blueshifted high-velocity gas traced by CO and CS is consistent with formation of SiO in shocks. Derived abundances of CO and HCO^(+) are consistent with quiescent and other star-forming regions while CS, HCN, and H2CO abundances indicate mild depletions within the condensation. Spectral energy distribution fits to S68 FIRS 1 indicate a modest luminosity (50-60 L_⊙), implying that it is a low-mass (0.5-3 M_⊙) young stellar object. Radio continuum observations of the triple source toward S68 FIRS 1 indicate that the lobe emission is varying on timescales ≤ 1 yr while the central component is relatively constant over ~14 yr. The nature of a newly detected compact emission region, S68 N, is less certain due to the absence of firm continuum detections; based on its low luminosity (<5 L_⊙) and strong molecular emission, S68 N may be prestellar subcondensation of gas and dust

Intrathecal colistin for drug-resistant Acinetobacter baumannii central nervous system infection: a case series and systematic review

AbstractTreatment limitations exist for drug-resistant Acinetobacter baumannii central nervous system (CNS) infection. We conducted a retrospective study and systematic literature review to identify patients with drug-resistant A. baumannii CNS infection who received primary or adjunct intrathecal or intraventricular (IT/IVT) colistin. In a case series of seven Thai patients and 17 patients identified in the literature, clinical and microbiological cure rates with IT/IVT colistin therapy were 83% and 92%, respectively. Three patients (13%) developed chemical ventriculitis and one (4%) experienced treatment-associated seizures. Death was associated with delayed IT/IVT colistin therapy compared to survival (mean time from diagnosis to IT/IVT colistin, 7 vs. 2 days; p 0.01). The only independent predictor of mortality was the severity of illness (APACHE II score > 19, adjusted odds ratio 49.5; 95% CI 1.7–1428.6; p 0.02). This case series suggests that administration of primary or adjunctive IT/IVT colistin therapy was effective for drug-resistant A. baumannii CNS infection

Molecular abundances and low-mass star formation. I: Si- and S-bearing species toward IRAS 16293-2422

Results from millimeter and submillimeter spectral line surveys of the protobinary source IRAS 16293-2422 are presented. Here we outline the abundances of silicon- and sulfur-containing species. A combination of rotation diagram and full statistical equilibrium/radiative transfer calculations is used to constrain the physical conditions toward IRAS 16293 and to construct its beam-averaged chemical composition over a 10-20" (1600-3200 AU) scale. The chemical complexity as judged by species such as SiO, OCS, and H_2S, is mtermedtate between that of dark molecular clouds such as Ll34N and hot molecular cloud cores such as Orion KL. From the richness of the spectra compared to other young stellar objects of similar luminosity, it is clear that molecular abundances do not scale simply with mass; rather, the chemistry is a strong function of evolutionary state, i.e., age

A molecular line study of NGC 1333/IRAS 4

Molecular line surveys and fully sampled spectral line maps at 1.3 and 0.87 mm are used to examine the physical and chemical characteristics of the extreme Class I sources IRAS 4A and 4B in the L1450/NGC 1333 molecular cloud complex. A very well collimated, jetlike molecular outflow emanates from IRAS 4A, with a dynamical age of a few thousand years. Symmetric, clumpy structure along the outflow lobes suggests that there is considerable variability in the mass-loss rate or wind velocity even at this young age. Molecular emission lines toward IRAS 4A and 4B are observed to be weak in the velocity range corresponding to quiescent material surrounding the young stellar objects (YSOs). Depletion factors of 10-20 are observed for αll molecules, including CO, even for very conservative mass estimates from the measured millimeter and submillimeter dust continuum. However, abundances scaled with respect to CO are similar to other dark molecular cloud cores. Such depletions could be mimicked by high dust optical depths or increased grain emissivities at the observing frequencies of 230 and 345 GHz, but the millimeter and submillimeter spectral energy distributions suggest that this is unlikely over the single-dish size scales of 5000-10,000 AU. Dense, outflowing gas is found to be kinematically, but not spatially, distinct from the quiescent material on these size scales. If CO is used as a chemical standard for the high-velocity gas, we find substantial enhancements in the abundances of several molecules in outflowing material, most notably CS, SiO, and CH_30H. The SiO emission is kinematically well displaced from the bulk cloud velocity and likely arises from directly shocked material. As is the case for CO, however, the outflow features from more volatile species are centered near the cloud velocity and are often characterized by quite low rotational temperatures. We suggest that grain-grain collisions induced by velocity shear zones surrounding the outflow axes transiently desorb the grain mantles, resulting in large abundance enhancements of selected species. Similar results have recently been obtained in several other low-mass YSOs, where the outflowing gas is often both kinematically and spatially distinct, and are illustrative of the ability of accretion and outflow processes to simultaneously modify the composition of the gas and dust surrounding young stars

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Mass Density Fluctuations in Quantum and Classical descriptions of Liquid Water

First principles molecular dynamics simulation protocol is established using revised functional of Perdew-Burke-Ernzerhof (revPBE) in conjunction with Grimme's third generation of dispersion (D3) correction to describe properties of water at ambient conditions. This study also demonstrates the consistency of the structure of water across both isobaric (NpT) and isothermal (NVT) ensembles. Going beyond the standard structural benchmarks for liquid water, we compute properties that are connected to both local structure and mass density uctuations that are related to concepts of solvation and hydrophobicity. We directly compare our revPBE results to the Becke-Lee-Yang-Parr (BLYP) plus Grimme dispersion corrections (D2) and both the empirical fixed charged model (SPC/E) and many body interaction potential model (MB-pol) to further our understanding of how the computed properties herein depend on the form of the interaction potential

The Psychological Impact of Austerity: A Briefing Paper

This report directly links cuts to public services with mental health problems. Well-established psychological research that explains these links already exists. However, this knowledge has been missing from the debate on austerity so far. Psychologists are often in a position to see the effects that social and economic changes have on people. We also occupy a relatively powerful position as professionals and therefore have an ethical responsibility to speak out about these effects. Key conclusions: Austerity policies have damaging psychological costs. Mental health problems are being created in the present, and further problems are being stored for the future. We have identified five ‘Austerity Ailments’. These are specific ways in which austerity policies impact on mental health: 1. Humiliation and shame 2. Fear and distrust 3. Instability and insecurity 4. Isolation and loneliness 5. Being trapped and powerless These experiences have been shown to increase mental health problems. Prolonged humiliation following a severe loss trebles the chance of being diagnosed with clinical depression. Job insecurity is as damaging for mental health as unemployment. Feeling trapped over the long term nearly trebles the chances of being diagnosed with anxiety and depression. Low levels of trust increase the chance of being diagnosed with depression by nearly 50 per cent. These five ‘ailments’ are indicators of problems in society, of poisonous public policy, weakness of social cohesion and inequalities in power and wealth. We also know what kind of society promotes good health. Key markers are that societies are equal, participatory and cohesive. Some important indicators of a psychologically healthy society are: 1. Agency 2. Security 3. Connection 4. Meaning 5. Trust Mental health isn’t just an individual issue. To create resilience and promote wellbeing, we need to look at the entirety of the social and economic conditions in which people live

The mechanisms underlying convergent evolution in the plumage patterns of birds

Convergent evolution is a central theme in biology. Birds are an ideal system to examine the mechanisms underlying convergent evolution. Although bird patterning is diverse, within-feather patterns have repeatedly converged on the same four types: mottled patterns, scales, bars and spots. Other avian patterns occur, e.g. stripes, but are rare. In my thesis I examine the four main mechanisms underlying convergent evolution in plumage patterns: evolutionary genetics, evolutionary development, natural selection for signaling and camouflage. Japanese quail (Coturnix japonica) is a model system in developmental biology. Examining the developmental basis of pattern formation using molecular techniques, the dorsal patterning of embryonic quail is likely due to activation of the melanocortin-1 receptor, which is a highly conserved pathway in vertebrates. I examined whether a reaction-diffusion based theoretical model of pattern formation may predict developmental constraint in two groups that have different lifestyles and spectacular patterns: waterfowl (Anseriformes) and gamebirds (Galliformes). Tracing the evolutionary trajectory of pattern evolution with Bayesian comparative modeling there was evidence for developmental constraint in pattern evolution. Adaptive explanations may also result in convergence. Cuckoo-hawk mimicry has been demonstrated in the common cuckoo (Cuculus canorus) and the Eurasian sparrowhawk (Accipiter nisus), but may be prevalent in Old World cuckoos. Randomly selecting a parasitic cuckoo from each genera of Old World cuckoos and <8 sympatric raptors, I quantified their barred patterns using digital image analysis and found that parasitism can explain convergent evolution in the patterns of parasitic cuckoos and raptors. Patterns may have evolved due to ecological selection. Examining the patterns of 80% of all avian species worldwide, I found that habitat does not predict patterning, and that all four patterns are found in all habitats. These results demonstrate that the mechanisms of convergent evolution are diverse, and that development and natural selection have contributed to pattern evolution.The Cambridge Commonwealth, European and International Trust, the John Stanley Gardiner Fund, and the Pembroke college graduate research fund