Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications

The role of the binary nucleation of sulfuric acid in aerosol formation and its implications for global warming is one of the fundamental unsettled questions in atmospheric chemistry. We have investigated the thermodynamics of sulfuric acid hydration using ab initio quantum mechanical methods. For H2SO4(H2O)n where n = 1–6, we used a scheme combining molecular dynamics configurational sampling with high-level ab initio calculations to locate the global and many low lying local minima for each cluster size. For each isomer, we extrapolated the Møller–Plesset perturbation theory (MP2) energies to their complete basis set (CBS) limit and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled harmonic vibrational frequencies. We found that ionic pair (HSO4–·H3O+)(H2O)n−1 clusters are competitive with the neutral (H2SO4)(H2O)n clusters for n ≥ 3 and are more stable than neutral clusters for n ≥ 4 depending on the temperature. The Boltzmann averaged Gibbs free energies for the formation of H2SO4(H2O)n clusters are favorable in colder regions of the troposphere (T = 216.65–273.15 K) for n = 1–6, but the formation of clusters with n ≥ 5 is not favorable at higher (T > 273.15 K) temperatures. Our results suggest the critical cluster of a binary H2SO4–H2O system must contain more than one H2SO4 and are in concert with recent findings(1) that the role of binary nucleation is small at ambient conditions, but significant at colder regions of the troposphere. Overall, the results support the idea that binary nucleation of sulfuric acid and water cannot account for nucleation of sulfuric acid in the lower troposphere.

Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications

The role of the binary nucleation of sulfuric acid in aerosol formation and its implications for global warming is one of the fundamental unsettled questions in atmospheric chemistry. We have investigated the thermodynamics of sulfuric acid hydration using ab initio quantum mechanical methods. For H2SO4(H2O)n where n = 1–6, we used a scheme combining molecular dynamics configurational sampling with high-level ab initio calculations to locate the global and many low lying local minima for each cluster size. For each isomer, we extrapolated the Møller–Plesset perturbation theory (MP2) energies to their complete basis set (CBS) limit and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled harmonic vibrational frequencies. We found that ionic pair (HSO4–·H3O+)(H2O)n−1clusters are competitive with the neutral (H2SO4)(H2O)n clusters for n ≥ 3 and are more stable than neutral clusters for n ≥ 4 depending on the temperature. The Boltzmann averaged Gibbs free energies for the formation of H2SO4(H2O)n clusters are favorable in colder regions of the troposphere (T = 216.65–273.15 K) for n = 1–6, but the formation of clusters with n ≥ 5 is not favorable at higher (T > 273.15 K) temperatures. Our results suggest the critical cluster of a binary H2SO4–H2O system must contain more than one H2SO4 and are in concert with recent findings(1) that the role of binary nucleation is small at ambient conditions, but significant at colder regions of the troposphere. Overall, the results support the idea that binary nucleation of sulfuric acid and water cannot account for nucleation of sulfuric acid in the lower troposphere.

Product Distributions Following Hyperthermal Collisions Between C2H4 And O(3P)

Transient Diode Laser Absorption Spectroscopy (TDLAS) was used to perform vibrational state population studies of the CO2 product from the hyperthermal reaction between C2H4 and O(3P) at room temperature using O3 as the O-atom precursor. Photodissociation of O3 using a frequency quadrupled Q-switch Nd:YAG laser pulse at 266 nm produced O(3P) atoms at high velocities which subsequently reacted with C2H4, producing several primary and secondary products including CO2. The CO2 product was detected using high-resolution TDLAS under five unique sets of reaction conditions. The vibrational distribution of the CO2 product did not follow a Boltzmann distribution at all five sets of conditions. The experiments showed a distribution in which there was a surprisingly high population in the (1000) (symmetric stretching) state compared with the other states probed, all of which contained bend excitation. In general, the CO2 population in the (1000) state was about 15-20% more populated than the Boltzmann distribution predicts. A possible explanation for this result may lie in the mechanism of CO2 evolution from the C2H4 + O(3P) reaction.

Transport model of the human Na+-coupled L-ascorbic acid (vitamin C) transporter SVCT1

Vitamin C (L-ascorbic acid) is an essential micronutrient that serves as an antioxidant and as a cofactor in many enzymatic reactions. Intestinal absorption and renal reabsorption of the vitamin is mediated by the epithelial apical L-ascorbic acid cotransporter SVCT1 (SLC23A1). We explored the molecular mechanisms of SVCT1-mediated L-ascorbic acid transport using radiotracer and voltage-clamp techniques in RNA-injected Xenopus oocytes. L-ascorbic acid transport was saturable (K(0.5) approximately 70 microM), temperature dependent (Q(10) approximately 5), and energized by the Na(+) electrochemical potential gradient. We obtained a Na(+)-L-ascorbic acid coupling ratio of 2:1 from simultaneous measurement of currents and fluxes. L-ascorbic acid and Na(+) saturation kinetics as a function of cosubstrate concentrations revealed a simultaneous transport mechanism in which binding is ordered Na(+), L-ascorbic acid, Na(+). In the absence of L-ascorbic acid, SVCT1 mediated pre-steady-state currents that decayed with time constants 3-15 ms. Transients were described by single Boltzmann distributions. At 100 mM Na(+), maximal charge translocation (Q(max)) was approximately 25 nC, around a midpoint (V(0.5)) at -9 mV, and with apparent valence approximately -1. Q(max) was conserved upon progressive removal of Na(+), whereas V(0.5) shifted to more hyperpolarized potentials. Model simulation predicted that the pre-steady-state current predominantly results from an ion-well effect on binding of the first Na(+) partway within the membrane electric field. We present a transport model for SVCT1 that will provide a framework for investigating the impact of specific mutations and polymorphisms in SLC23A1 and help us better understand the contribution of SVCT1 to vitamin C metabolism in health and disease.

Proteins in silico-modeling and sampling

Proteins are linear chain molecules made out of amino acids. Only when they fold to their native states, they become functional. This dissertation aims to model the solvent (environment) effect and to develop & implement enhanced sampling methods that enable a reliable study of the protein folding problem in silico. We have developed an enhanced solvation model based on the solution to the Poisson-Boltzmann equation in order to describe the solvent effect. Following the quantum mechanical Polarizable Continuum Model (PCM), we decomposed net solvation free energy into three physical terms– Polarization, Dispersion and Cavitation. All the terms were implemented, analyzed and parametrized individually to obtain a high level of accuracy. In order to describe the thermodynamics of proteins, their conformational space needs to be sampled thoroughly. Simulations of proteins are hampered by slow relaxation due to their rugged free-energy landscape, with the barriers between minima being higher than the thermal energy at physiological temperatures. In order to overcome this problem a number of approaches have been proposed of which replica exchange method (REM) is the most popular. In this dissertation we describe a new variant of canonical replica exchange method in the context of molecular dynamic simulation. The advantage of this new method is the easily tunable high acceptance rate for the replica exchange. We call our method Microcanonical Replica Exchange Molecular Dynamic (MREMD). We have described the theoretical frame work, comment on its actual implementation, and its application to Trp-cage mini-protein in implicit solvent. We have been able to correctly predict the folding thermodynamics of this protein using our approach.

A 45nm CMOS DESIGN OF NEUROMORPHIC SYSTEM

Neuromorphic computing has become an emerging field in wide range of applications. Its challenge lies in developing a brain-inspired architecture that can emulate human brain and can work for real time applications. In this report a flexible neural architecture is presented which consists of 128 X 128 SRAM crossbar memory and 128 spiking neurons. For Neuron, digital integrate and fire model is used. All components are designed in 45nm technology node. The core can be configured for certain Neuron parameters, Axon types and synapses states and are fully digitally implemented. Learning for this architecture is done offline. To train this circuit a well-known algorithm Restricted Boltzmann Machine (RBM) is used and linear classifiers are trained at the output of RBM. Finally, circuit was tested for handwritten digit recognition application. Future prospects for this architecture are also discussed.

Quartärbotanische Untersuchungen zur Vegetationsgeschichte der Alpe d'Essertse (Hérémence, Wallis)

Afin d'étudier l'histoire de la végétation de l'Alpe d'Essertse, des sondages ont été effectués dans le Gouillé Rion, un étang situé à 2343 m d'altitude. Les grains de pollen contenus dans le sédiment lacustre ont été analysés palynologiquement. Le diagramme pollinique montre qu'après le retrait des glaciers vers 13000 BP (Before Present), l'Alpe d'Essertse fut colonisée par une végétation alpine et une végétation d'éboulis. Entre 9500 et 3600 BP le mélèze (Larix decidua) et l'arole (Pinus cembra) formaient une forêt qui atteignait au moins 2343 m. A partir de 5000 BP la forêt s'ouvrit et la limite de la forêt commença à s'abaisser. Des buissons d'aune vert (Alnus viridis) remplacèrent peut à peu la forêt. Entre 1700 et 900 BP seulement, cette végétation apparentée aux forêts fit place aux prés et pâturages. Seul l'utilisation d'autres méthodes permet d'estimer la limite d'altitude maximale atteinte par la forêt au cours de l'holocène: pour l'Alpe d'Essertse des charbons trouvés dans le sol, ainsi que des bioséquences pédologiques suggèrent une limite de la forêt maximale entre 2400 et 2450 m d'altitude.

The Interstellar Neutral He haze in the heliosphere: what can we learn?

Neutral interstellar helium has been observed by the Interstellar Boundary Explorer (IBEX) since 2009, with a signal-to-noise ratio well above 1000. Because of the geometry of the observations, the signal observed from January to March each year is the easiest to identify. However, as we show via simulations, the portion of the signal in the range of intensities from 10(-3) to 10(-2) of the peak value, previously mostly left out from the analysis, may provide important information about the details of the distribution function of interstellar He gas in front of the heliosphere. In particular, these observations may inform us about possible departures of the parent interstellar He population from equilibrium. We compare the expected distribution of the signal for the canonical assumption of a single Maxwell-Boltzmann population with the distributions for a superposition of the Maxwell-Boltzmann primary population and the recently discovered Warm Breeze, and for a single primary population given by a kappa function. We identify the regions on the sky where the differences between those cases are expected to be the most visible against the background. We discuss the diagnostic potential of the fall peak of the interstellar signal, reduced by a factor of 50 due to the Compton-Getting effect but still above the detection limit of IBEX. We point out the strong energy dependence of the fall signal and suggest that searching for this signal in the data could bring an independent assessment of the low-energy measurement threshold of the IBEX-Lo sensor.

Der Kampf um Tsingtau : eine Episode aus dem Weltkrieg 1914/1918 nach Tagebuchblättern

von Waldemar Vollerthun, Konteradmiral a.D.

Pollen records of 11 profiles from Wendland in northern Germany

1) Ingesamt 11 Profile aus sechs Mooren und Seen im Gebiet des Hannoverschen Wendlandes wurden pollenanalytisch untersucht. Die Ablagerungen umfassen den Zeitraum vom Beginn der Älteren Tundrenzeit bis zur Gegenwart. 2) Die Waldgeschichte des Hannoverschen Wendlandes weist teils Merkmale der atlantisch geprägten Gebiete Nordwestdeutschlands, teils solche des kontinental beeinflußten nordostdeutschen Raumes auf und nimmt damit eine Zwischenstellung ein. 3) Die Kiefer wandert zu Beginn der Allerödzeit ein, d.h. später als im mecklenburgisch-märkischen Gebiet und im mitteldeutschen Trockengebiet. Im Verlauf der Allerödzeit bildeten sich hier wie dort lichte Kiefern-Birken-Wälder aus. 4) In der Jüngeren Tundrenzeit fand zunächst nur eine geringe Auflichtung der Wälder statt, und die Kiefer überwog weiterhin. Erst im späteren Verlauf dieser stadialen Phase breitete sich die Birke aus und verdrängte die Kiefer. Der späte Rückgang der Kiefer stellt eine Parallele zu der Entwicklung in Südostmecklenburg und in der Altmark dar. Die Abgrenzung dieser Phasen in der Jüngeren Tundrenzeit ist durch eine 14C-Datierung gesichert. 5) Noch im Atlantikum ähneln die Diagramme aus dem Gartower Talsandgebiet im Osten des Wendlandes in ihren hohen Kiefernanteilen denen der Sandergebiete in Brandenburg. Die Diagramme aus dem Moränengebiet des westlichen Wendlandes schließen dagegen mehr an die der östlichen Lüneburger Heide und des Hamburger Gebietes an. Dieser Unterschied wird auf edaphische Unterschiede zurückgeführt. 6) Seit dem frühen Subboreal glich auch die Vegetation des Gartower Gebietes mehr den buchenarmen Waldgesellschaften auf sauren Sandböden, wie sie im atlantischen Westen vorkommen. Die Kiefern sind fast ganz aus dem Waldbild verschwunden, wobei der rasche Rückgang zu Beginn des Subboreals sicher zu einem wesentlichen Teil vom Menschen beeinflusst worden ist. Die anschließende kiefernarme Zeit dauerte im gesamten Wendland bis zum Beginn der Kieferaufforstungen in der Neuzeit. 7) In allen untersuchten Diagrammen ist etwa seit dem Subboreal eine Besiedlung nachzuweisen. Diese muß im Osten des Wendlandes intensiver gewesen sein als im Westen. Es lassen sich Phasen geringer und intensiver Besiedlung nachweisen. 8) Seit Beginn des Subboreals ist das Waldbild schon so stark vom Menschen beeinflusst, dass die Ausbreitungsgeschichte der Laubwaldarten nicht ohne Berücksichtigung der Siedlungsphasen diskutiert werden kann. Besonders im Westen bestand eine ausgedehnte Lindenphase, die durch eine Siedlungszeit (Bronzezeit) beendet wurde. Beim folgenden Rückgang der Siedlungsintensität breitet sich bevorzugt die Hainbuche aus, die dann bei der nächsten Besiedlungsphase (Eisenzeit) zurückging. Erst danach erfolgte die maximale Rotbuchenausbreitung, die nur im Westteil des Wendlandes bedeutende Ausmaße zeigte, während im Ostteil rot- und hainbuchenreiche Eichenwälder entstanden. 9) Seit Beginn der mittelalterlichen Besiedlung ist dann der Eingriff des Menschen so stark gewesen, dass die edaphisch bedingten Unterschiede zwischen Moränen- und Sandergebieten im Pollenspektrum verwischt wurden. Sowohl die buchenreichen Wälder des westlichen als auch die buchenarmen Wälder des mittleren und des östlichen Teilgebietes müssen zu fast reinen Eichenwäldern geworden sein. 10) Calluna-Heiden sind im östlichen Wendland schon in vorgeschichtlicher Zeit nachzuweisen. Im Mittelalter und in der Neuzeit treten sie im gesamten Wendland auf. Etwa im 18. und 19. Jahrhundert war die Ausdehnung der Heideflächen am größten. Erst danach wurden sie im Zuge der Kiefernaufforstungen bis auf geringe Reste verdrängt. 11) Während in der spätglazialen Vegetation Juniperus auftritt, ist der Wacholder sowohl in vorgeschichtlicher als auch in geschichtlicher Zeit - im Gegensatz zur Lüneburger Heide - wohl niemals ein Bestandteil der anthropogenen Calluna-Heiden gewesen.

Measured Stark widths of several spectral lines of Pb III

The Stark full widths at half of the maximal line intensity (FWHM, ω) have been measured for 25 spectrallines of PbIII (15 measured for the first time) arising from the 5d106s8s, 5d106s7p, 5d106s5f and 5d106s5g electronic configurations, in a lead plasma produced by ablation with a Nd:YAG laser. The optical emission spectroscopy from a laser-induced plasma generated by a 10 640 Å radiation, with an irradiance of 2 × 1010 W cm− 2 on a lead target (99.99% purity) in an atmosphere of argon was analysed in the wavelength interval between 2000 and 7000 Å. The broadening parameters were obtained with the target placed in argon atmosphere at 6 Torr and 400 ns after each laser light pulse, which provides appropriate measurement conditions. A Boltzmann plot was used to obtain the plasma temperature (21,400 K) and published values of the Starkwidths in Pb I, Pb II and PbIII to obtain the electron number density (7 × 1016 cm− 3); with these values, the plasma composition was determined by means of the Saha equation. Local Thermodynamic Equilibrium (LTE) conditions and plasma homogeneity has been checked. Special attention was dedicated to the possible self-absorption of the different transitions. Comparison of the new results with recent available data is also presented.

3D Soil Images Structure Quantification using Relative Entropy

Soil voids manifest the cumulative effect of local pedogenic processes and ultimately influence soil behavior - especially as it pertains to aeration and hydrophysical properties. Because of the relatively weak attenuation of X-rays by air, compared with liquids or solids, non-disruptive CT scanning has become a very attractive tool for generating three-dimensional imagery of soil voids. One of the main steps involved in this analysis is the thresholding required to transform the original (greyscale) images into the type of binary representation (e.g., pores in white, solids in black) needed for fractal analysis or simulation with Lattice?Boltzmann models (Baveye et al., 2010). The objective of the current work is to apply an innovative approach to quantifying soil voids and pore networks in original X-ray CT imagery using Relative Entropy (Bird et al., 2006; Tarquis et al., 2008). These will be illustrated using typical imagery representing contrasting soil structures. Particular attention will be given to the need to consider the full 3D context of the CT imagery, as well as scaling issues, in the application and interpretation of this index.