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.

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.

Ay Pitágoras! : acerca de las determinaciones sociales en el surgimiento de las matemáticas

El artículo pretende mostrar a partir del ejemplo del descubrimiento del Teorema de Pitágoras, cómo las ideas sociales de una época determinada, para nuestro caso las de la sociedad griega del siglo V a.C., intervienen en el proceso de formación científica ya sea para facilitar o bloquear su desarrollo. El caso de las matemáticas pitagóricas es significativo al respecto; su análisis no deja de ser un punto paradigmático en la historia de las ciencias desde el punto de vista de la sociología.

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.

A recursive algorithm to compute a basis of a similarity

Se definen conceptos y se aplica el teorema de Valverde para escribir un algoritmo que computa bases de similaridades. This paper studies sorne theory and methods to build a representation theorem basis of a similarity from the basis of its subsimilarities, providing an alternative recursive method to compute the basis of a similarity.

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.

Medidas autosemejantes en el plano, momentos y matrices de Hessenberg

La tesis MEDIDAS AUTOSEMEJANTES EN EL PLANO, MOMENTOS Y MATRICES DE HESSENBERG se enmarca entre las áreas de la teoría geométrica de la medida, la teoría de polinomios ortogonales y la teoría de operadores. La memoria aborda el estudio de medidas con soporte acotado en el plano complejo vistas con la óptica de las matrices infinitas de momentos y de Hessenberg asociadas a estas medidas que en la teoría de los polinomios ortogonales las representan. En particular se centra en el estudio de las medidas autosemejantes que son las medidas de equilibrio definidas por un sistema de funciones iteradas (SFI). Los conjuntos autosemejantes son conjuntos que tienen la propiedad geométrica de descomponerse en unión de piezas semejantes al conjunto total. Estas piezas pueden solaparse o no, cuando el solapamiento es pequeño la teoría de Hutchinson [Hut81] funciona bien, pero cuando no existen restricciones falla. El problema del solapamiento consiste en controlar la medida de este solapamiento. Un ejemplo de la complejidad de este problema se plantea con las convoluciones infinitas de distribuciones de Bernoulli, que han resultado ser un ejemplo de medidas autosemejantes en el caso real. En 1935 Jessen y A. Wintner [JW35] ya se planteaba este problema, lejos de ser sencillo ha sido estudiado durante más de setenta y cinco años y siguen sin resolverse las principales cuestiones planteadas ya por A. Garsia [Gar62] en 1962. El interés que ha despertado este problema así como la complejidad del mismo está demostrado por las numerosas publicaciones que abordan cuestiones relacionadas con este problema ver por ejemplo [JW35], [Erd39], [PS96], [Ma00], [Ma96], [Sol98], [Mat95], [PS96], [Sim05],[JKS07] [JKS11]. En el primer capítulo comenzamos introduciendo con detalle las medidas autosemejante en el plano complejo y los sistemas de funciones iteradas, así como los conceptos de la teoría de la medida necesarios para describirlos. A continuación se introducen las herramientas necesarias de teoría de polinomios ortogonales, matrices infinitas y operadores que se van a usar. En el segundo y tercer capítulo trasladamos las propiedades geométricas de las medidas autosemejantes a las matrices de momentos y de Hessenberg, respectivamente. A partir de estos resultados se describen algoritmos para calcular estas matrices a partir del SFI correspondiente. Concretamente, se obtienen fórmulas explícitas y algoritmos de aproximación para los momentos y matrices de momentos de medidas fractales, a partir de un teorema del punto fijo para las matrices. Además utilizando técnicas de la teoría de operadores, se han extendido al plano complejo los resultados que G. Mantica [Ma00, Ma96] obtenía en el caso real. Este resultado es la base para definir un algoritmo estable de aproximación de la matriz de Hessenberg asociada a una medida fractal u obtener secciones finitas exactas de matrices Hessenberg asociadas a una suma de medidas. En el último capítulo, se consideran medidas, μ, más generales y se estudia el comportamiento asintótico de los autovalores de una matriz hermitiana de momentos y su impacto en las propiedades de la medida asociada. En el resultado central se demuestra que si los polinomios asociados son densos en L2(μ) entonces necesariamente el autovalor mínimo de las secciones finitas de la matriz de momentos de la medida tiende a cero. ABSTRACT The Thesis work “Self-similar Measures on the Plane, Moments and Hessenberg Matrices” is framed among the geometric measure theory, orthogonal polynomials and operator theory. The work studies measures with compact support on the complex plane from the point of view of the associated infinite moments and Hessenberg matrices representing them in the theory of orthogonal polynomials. More precisely, it concentrates on the study of the self-similar measures that are equilibrium measures in a iterated functions system. Self-similar sets have the geometric property of being decomposable in a union of similar pieces to the complete set. These pieces can overlap. If the overlapping is small, Hutchinson’s theory [Hut81] works well, however, when it has no restrictions, the theory does not hold. The overlapping problem consists in controlling the measure of the overlap. The complexity of this problem is exemplified in the infinite convolutions of Bernoulli’s distributions, that are an example of self-similar measures in the real case. As early as 1935 [JW35], Jessen and Wintner posed this problem, that far from being simple, has been studied during more than 75 years. The main cuestiones posed by Garsia in 1962 [Gar62] remain unsolved. The interest in this problem, together with its complexity, is demonstrated by the number of publications that over the years have dealt with it. See, for example, [JW35], [Erd39], [PS96], [Ma00], [Ma96], [Sol98], [Mat95], [PS96], [Sim05], [JKS07] [JKS11]. In the first chapter, we will start with a detailed introduction to the self-similar measurements in the complex plane and to the iterated functions systems, also including the concepts of measure theory needed to describe them. Next, we introduce the necessary tools from orthogonal polynomials, infinite matrices and operators. In the second and third chapter we will translate the geometric properties of selfsimilar measures to the moments and Hessenberg matrices. From these results, we will describe algorithms to calculate these matrices from the corresponding iterated functions systems. To be precise, we obtain explicit formulas and approximation algorithms for the moments and moment matrices of fractal measures from a new fixed point theorem for matrices. Moreover, using techniques from operator theory, we extend to the complex plane the real case results obtained by Mantica [Ma00, Ma96]. This result is the base to define a stable algorithm that approximates the Hessenberg matrix associated to a fractal measure and obtains exact finite sections of Hessenberg matrices associated to a sum of measurements. In the last chapter, we consider more general measures, μ, and study the asymptotic behaviour of the eigenvalues of a hermitian matrix of moments, together with its impact on the properties of the associated measure. In the main result we demonstrate that, if the associated polynomials are dense in L2(μ), then necessarily follows that the minimum eigenvalue of the finite sections of the moments matrix goes to zero.