Thermal dissociation of dipositronium: path integral Monte Carlo approach

Path integral Monte Carlo simulation of the dipositronium "molecule" Ps$_2$ reveals its surprising thermal instability. Although, the binding energy is $\sim 0.4$ eV, due to the strong temperature dependence of its free energy Ps$_2$ dissociates, or does not form, above $\sim 1000$ K, except for high densities where a small fraction of molecules are in equilibrium with Ps atoms. This prediction is consistent with the recently reported first observation of stable Ps$_2$ molecules by Cassidy & Mills Jr., Nature {\bf 449}, 195 (07), and Phys.Rev.Lett. {\bf 100}, 013401 (08); at temperatures below 1000 K. The relatively sharp transition from molecular to atomic equilibrium, that we find, remains to be experimentally verified. To shed light on the origin of the large entropy factor in free energy we analyze the nature of interatomic interactions of these strongly correlated quantum particles. The conventional diatomic potential curve is given by the van der Waals interaction at large distances, but due to the correlations and high delocalization of constituent particles the concept of potential curve becomes ambiguous at short atomic distances.Comment: Submitted to the Physical Review Letter

Finite temperature quantum statistics of H3+_3^+ molecular ion

Full quantum statistical $NVT$ simulation of the five-particle system H$_3^+$ has been carried out using the path integral Monte Carlo method. Structure and energetics is evaluated as a function of temperature up to the thermal dissociation limit. The weakly density dependent dissociation temperature is found to be around $4000$ K. Contributions from the quantum dynamics and thermal motion are sorted out by comparing differences between simulations with quantum and classical nuclei. The essential role of the quantum description of the protons is established.Comment: submitted to the Journal of Chemical Physic

Few-body reference data for multicomponent formalisms: Light nuclei molecules

We present full quantum statistical energetics of some electron-light nuclei systems. This is accomplished with the path integral Monte Carlo method. The effects on energetics arising from the change in the nuclear mass are studied. The obtained results may serve as reference data for the multicomponent density functional theory calculations of light nuclei system. In addition, the results reported here will enable better fitting of todays electron-nuclear energy functionals, for which the description of light nuclei is most challenging, in particular

Annual cycle of volatile organic compound exchange between a boreal pine forest and the atmosphere

Long-term flux measurements of volatile organic compounds (VOC) over boreal forests are rare, although the forests are known to emit considerable amounts of VOCs into the atmosphere. Thus, we measured fluxes of several VOCs and oxygenated VOCs over a Scots-pine-dominated boreal forest semi-continuously between May 2010 and December 2013. The VOC profiles were obtained with a proton transfer reaction mass spectrometry, and the fluxes were calculated using vertical concentration profiles and the surface layer profile method connected to the Monin-Obukhov similarity theory. In total fluxes that differed significantly from zero on a monthly basis were observed for 13 out of 27 measured masses. Monoterpenes had the highest net emission in all seasons and statistically significant positive fluxes were detected from March until October. Other important compounds emitted were methanol, ethanol+ formic acid, acetone and isoprene+ methylbutenol. Oxygenated VOCs showed also deposition fluxes that were statistically different from zero. Isoprene+ methylbutenol and monoterpene fluxes followed well the traditional isoprene algorithm and the hybrid algorithm, respectively. Emission potentials of monoterpenes were largest in late spring and autumn which was possibly driven by growth processes and decaying of soil litter, respectively. Conversely, largest emission potentials of isoprene+ methylbutenol were found in July. Thus, we concluded that most of the emissions of m/z 69 at the site consisted of isoprene that originated from broadleaved trees. Methanol had deposition fluxes especially before sunrise. This can be connected to water films on surfaces. Based on this assumption, we were able to build an empirical algorithm for bi-directional methanol exchange that described both emission term and deposition term. Methanol emissions were highest in May and June and deposition level increased towards autumn, probably as a result of increasing relative humidity levels leading to predominance of deposition.Peer reviewe

Vibrational signatures for low-energy intermediate-sized Si clusters

We report low-energy locally stable structures for the clusters Si20 and Si21. The structures were obtained by performing geometry optimizations within the local density approximation. Our calculated binding energies for these clusters are larger than any previously reported for this size regime. To aid in the experimental identification of the structures, we have computed the full vibrational spectra of the clusters, along with the Raman and IR activities of the various modes using a recently developed first-principles technique. These represent, to our knowledge, the first calculations of Raman and IR spectra for Si clusters of this size

Transgenerational Effects of Heavy Metal Pollution on Immune Defense of the Blow Fly Protophormia terraenovae

Recently environmental conditions during early parental development have been found to have transgenerational effects on immunity and other condition-dependent traits. However, potential transgenerational effects of heavy metal pollution have not previously been studied. Here we show that direct exposure to heavy metal (copper) upregulates the immune system of the blow fly, Protophormia terraenovae, reared in copper contaminated food. In the second experiment, to test transgenerational effects of heavy metal, the parental generation of the P. terraenovae was reared in food supplemented with copper, and the immunocompetence of their offspring, reared on uncontaminated food, was measured. Copper concentration used in this study was, in the preliminary test, found to have no effect on mortality of the flies. Immunity was tested on the imago stage by measuring encapsulation response against an artificial antigen, nylon monofilament. We found that exposure to copper during the parental development stages through the larval diet resulted in immune responses that were still apparent in the next generation that was not exposed to the heavy metal. We found that individuals reared on copper-contaminated food developed more slowly compared with those reared on uncontaminated food. The treatment groups did not differ in their dry body mass. However, parental exposure to copper did not have an effect on the development time or body mass of their offspring. Our study suggests that heavy metal pollution has positive feedback effect on encapsulation response through generations which multiplies the harmful effects of heavy metal pollution in following generations

The Arabidopsis NOT4A E3 ligase promotes PGR3 expression and regulates chloroplast translation

Chloroplast function requires the coordinated action of nuclear- and chloroplast-derived proteins, including several hundred nuclear-encoded pentatricopeptide repeat (PPR) proteins that regulate plastid mRNA metabolism. Despite their large number and importance, regulatory mechanisms controlling PPR expression are poorly understood. Here we show that the Arabidopsis NOT4A ubiquitin-ligase positively regulates the expression of PROTON GRADIENT REGULATION 3 (PGR3), a PPR protein required for translating several thylakoid-localised photosynthetic components and ribosome subunits within chloroplasts. Loss of NOT4A function leads to a strong depletion of cytochrome b6f and NAD(P)H dehydrogenase (NDH) complexes, as well as plastid 30 S ribosomes, which reduces mRNA translation and photosynthetic capacity, causing pale-yellow and slow-growth phenotypes. Quantitative transcriptome and proteome analysis of the not4a mutant reveal it lacks PGR3 expression, and that its molecular defects resemble those of a pgr3 mutant. Furthermore, we show that normal plastid function is restored to not4a through transgenic PGR3 expression. Our work identifies NOT4A as crucial for ensuring robust photosynthetic function during development and stress-response, through promoting PGR3 production and chloroplast translatio

The impacts of environmental warming on Odonata: a review

Climate change brings with it unprecedented rates of increase in environmental temperature, which will have major consequences for the earth's flora and fauna. The Odonata represent a taxon that has many strong links to this abiotic factor due to its tropical evolutionary history and adaptations to temperate climates. Temperature is known to affect odonate physiology including life-history traits such as developmental rate, phenology and seasonal regulation as well as immune function and the production of pigment for thermoregulation. A range of behaviours are likely to be affected which will, in turn, influence other parts of the aquatic ecosystem, primarily through trophic interactions. Temperature may influence changes in geographical distributions, through a shifting of species' fundamental niches, changes in the distribution of suitable habitat and variation in the dispersal ability of species. Finally, such a rapid change in the environment results in a strong selective pressure towards adaptation to cope and the inevitable loss of some populations and, potentially, species. Where data are lacking for odonates, studies on other invertebrate groups will be considered. Finally, directions for research are suggested, particularly laboratory studies that investigate underlying causes of climate-driven macroecological patterns

Sex, War, and Disease: The Role of Parasite Infection on Weapon Development and Mating Success in a Horned Beetle (Gnatocerus cornutus)

While parasites and immunity are widely believed to play important roles in the evolution of male ornaments, their potential influence on systems where male weaponry is the object of sexual selection is poorly understood. We experimentally infect larval broad-horned flour beetles with a tapeworm and study the consequent effects on: 1) adult male morphology 2) male-male contests for mating opportunities, and 3) induction of the innate immune system. We find that infection significantly reduces adult male size in ways that are expected to reduce mating opportunities in nature. The sum of our morphological, competition, and immunological data indicate that during a life history stage where no new resources are acquired, males allocate their finite resources in a way that increases future mating potential

Wintertime subarctic new particle formation from Kola Peninsula sulfur emissions

The metallurgical industry in the Kola Peninsula, north-west Russia, form, after Norilsk, Siberia, the second largest source of air pollution in the Arctic and subarctic domain. Sulfur dioxide (SO2/emissions from the ore smelters are transported to wide areas, including Finnish Lapland. We performed investigations on concentrations of SO2, aerosol precursor vapours, aerosol and ion cluster size distributions together with chemical composition measurements of freshly formed clusters at the SMEAR I station in Finnish Lapland relatively close (similar to 300 km) to the Kola Peninsula industrial sites during the winter 2019-2020. We show that highly concentrated SO2 from smelter emissions is converted to sulfuric acid (H2SO4/in sufficient concentrations to drive new particle formation hundreds of kilometres downwind from the emission sources, even at very low solar radiation intensities. Observed new particle formation is primarily initiated by H2SO4-ammonia (negative-)ion-induced nucleation. Particle growth to cloud condensation nuclei (CCN) sizes was concluded to result from sulfuric acid condensation. However, air mass advection had a large role in modifying aerosol size distributions, and other growth mechanisms and condensation of other compounds cannot be fully excluded. Our results demonstrate the dominance of SO2 emissions in controlling wintertime aerosol and CCN concentrations in the subarctic region with a heavily polluting industry.Peer reviewe