Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals

We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an σ framework.

Ability of the PM3 Quantum Mechanical Method to Model Intermolecular Hydrogen Bonding between Neutral Molecules

The PM3 semiempirical quantum-mechanical method was found to systematically describe intermolecular hydrogen bonding in small polar molecules. PM3 shows charge transfer from the donor to acceptor molecules on the order of 0.02-0.06 units of charge when strong hydrogen bonds are formed. The PM3 method is predictive; calculated hydrogen bond energies with an absolute magnitude greater than 2 kcal mol-' suggest that the global minimum is a hydrogen bonded complex; absolute energies less than 2 kcal mol-' imply that other van der Waals complexes are more stable. The geometries of the PM3 hydrogen bonded complexes agree with high-resolution spectroscopic observations, gas electron diffraction data, and high-level ab initio calculations. The main limitations in the PM3 method are the underestimation of hydrogen bond lengths by 0.1-0.2 for some systems and the underestimation of reliable experimental hydrogen bond energies by approximately 1-2 kcal mol-l. The PM3 method predicts that ammonia is a good hydrogen bond acceptor and a poor hydrogen donor when interacting with neutral molecules. Electronegativity differences between F, N, and 0 predict that donor strength follows the order F > 0 > N and acceptor strength follows the order N > 0 > F. In the calculations presented in this article, the PM3 method mirrors these electronegativity differences, predicting the F-H- - -N bond to be the strongest and the N-H- - -F bond the weakest. It appears that the PM3 Hamiltonian is able to model hydrogen bonding because of the reduction of two-center repulsive forces brought about by the parameterization of the Gaussian core-core interactions. The ability of the PM3 method to model intermolecular hydrogen bonding means reasonably accurate quantum-mechanical calculations can be applied to small biologic systems.

Energetic neutral atom imaging of the lunar surface

Since the Moon is not shielded by a global magnetic field or by an atmosphere, solar wind plasma impinges onto the lunar surface almost unhindered. Until recently, it was assumed that almost all of the impinging solar wind ions are absorbed by the surface. However, recent Interstellar Boundary Explorer, Chandrayaan-1, and Kaguya observations showed that the interaction process between the solar wind ions and the lunar surface is more complex than previously assumed. In contrast to previous assumptions, a large fraction of the impinging solar wind ions is backscattered as energetic neutral atoms. Using the complete Chandrayaan-1 Energetic Neutral Analyzer data set, we compute a global solar wind reflection ratio of 0.16 ± 0.05 from the lunar surface. Since these backscattered neutral particles are not affected by any electric or magnetic fields, each particle's point of origin on the lunar surface can be determined in a straight-forward manner allowing us to create energetic neutral atom maps of the lunar surface. The energetic neutral atom measurements recorded by the Chandrayaan-1 Energetic Neutral Analyzer cover ˜89% of the lunar surface, whereby the lunar farside is almost completely covered. We analyzed all available energetic neutral atom measurements recorded by the Chandrayaan-1 Energetic Neutral Analyzer to create the first global energetic neutral hydrogen maps of the lunar surface.

Lunar energetic neutral atom (ENA) spectra measured by the interstellar boundary explorer (IBEX)

The solar wind continuously flows out from the Sun, filling interplanetary space and directly interacting with the surfaces of small planetary bodies and other objects throughout the solar system. A significant fraction of these ions backscatter from the surface as energetic neutral atoms (ENAs). The first observations of these ENA emissions from the Moon were recently reported from the Interstellar Boundary Explorer (IBEX). These observations yielded a lunar ENA albedo of ˜10% and showed that the Moon reflects ˜150 metric tons of neutral hydrogen per year. More recently, a survey of the first 2.5 years of IBEX observations of lunar ENAs was conducted for times when the Moon was in the solar wind. Here, we present the first IBEX ENA observations when the Moon is inside the terrestrial magnetosheath and compare them with observations when the Moon is in the solar wind. Our analysis shows that: (1) the ENA intensities are on average higher when the Moon is in the magnetosheath, (2) the energy spectra are similar above ~0.6* solar wind energy but below there are large differences of the order of a factor of 10, (3) the energy spectra resemble a power law with a "hump" at ˜0.6 * solar wind energy, and (4) this "hump" is broader when the Moon is in the magnetosheath. We explore potential scenarios to explain the differences, namely the effects of the topography of the lunar surface and the consequences of a very different Mach number in the solar wind versus in the magnetosheath.

Remote energetic neutral atom imaging of electric potential over a lunar magnetic anomaly

The formation of electric potential over lunar magnetized regions is essential for understanding fundamental lunar science, for understanding the lunar environment, and for planning human exploration on the Moon. A large positive electric potential was predicted and detected from single point measurements. Here, we demonstrate a remote imaging technique of electric potential mapping at the lunar surface, making use of a new concept involving hydrogen neutral atoms derived from solar wind. We apply the technique to a lunar magnetized region using an existing dataset of the neutral atom energy spectrometer SARA/CENA on Chandrayaan-1. Electrostatic potential larger than +135 V inside the Gerasimovic anomaly is confirmed. This structure is found spreading all over the magnetized region. The widely spread electric potential can influence the local plasma and dust environment near the magnetic anomaly.

Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4) or δ2H(CH4)) 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4) measurements in (ice core) air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping), and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping), both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP) – of air) with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4) of about 6 mL (STP) or about 500 pmol of pure CH4.

Backscattered energetic neutral atoms from the Moon in the Earth's plasma sheet observed by Chandarayaan-1/Sub-keV Atom Reflecting Analyzer instrument

We present the observations of energetic neutral atoms (ENAs) produced at the lunar surface in the Earth's magnetotail. When the Moon was located in the terrestrial plasma sheet, Chandrayaan-1 Energetic Neutrals Analyzer (CENA) detected hydrogen ENAs from the Moon. Analysis of the data from CENA together with the Solar Wind Monitor (SWIM) onboard Chandrayaan-1 reveals the characteristic energy of the observed ENA energy spectrum (the e-folding energy of the distribution function) ∼100 eV and the ENA backscattering ratio (defined as the ratio of upward ENA flux to downward proton flux) <∼0.1. These characteristics are similar to those of the backscattered ENAs in the solar wind, suggesting that CENA detected plasma sheet particles backscattered as ENAs from the lunar surface. The observed ENA backscattering ratio in the plasma sheet exhibits no significant difference in the Southern Hemisphere, where a large and strong magnetized region exists, compared with that in the Northern Hemisphere. This is contrary to the CENA observations in the solar wind, when the backscattering ratio drops by ∼50% in the Southern Hemisphere. Our analysis and test particle simulations suggest that magnetic shielding of the lunar surface in the plasma sheet is less effective than in the solar wind due to the broad velocity distributions of the plasma sheet protons.

First πK atom lifetime and πK scattering length measurements

The results of a search for hydrogen-like atoms consisting of π∓K±π∓K± mesons are presented. Evidence for πK atom production by 24 GeV/c protons from CERN PS interacting with a nickel target has been seen in terms of characteristic πK pairs from their breakup in the same target (178±49178±49) as well as in terms of produced πK atoms (653±42653±42). Using these results, the analysis yields a first value for the πK atom lifetime of View the MathML sourceτ=(2.5−1.8+3.0) fs and a first measurement of the S-wave isospin-odd πK scattering length View the MathML source|a0−|=13|a1/2−a3/2|=(0.11−0.04+0.09)Mπ−1 (aIaI for isospin I).

LCAO-MO's are not Eigenfunctions of the H_2^+ Hamiltonian

A simple LCAO-MO for the hydrogen molecule cation is tested for eigenfunctionality and found to be flawed.

Hydrogen isotope composition of pore waters and interlayer water in sediments of ODP Leg 129 holes

Hydrogen isotope compositions have been measured on pore waters from sediments of Leg 129 sites in the Pigafetta and East Mariana basins (central western Pacific). Total water (pore + sorbed waters) contents and their dD have been analyzed for three samples that contain smectite but no zeolite so that sorbed water can be attributed to interlayer water. The H budget for pore and total waters implies that interlayer water is 20 per mil to 30 per mil depleted in D compared to pore water. Because the interlayer/total water molar ratio (0.25 to 0.5) in smectitic sediments is very high, interlayer water represents an important reservoir of D-depleted water in sediments. dD depth profiles for pore water at Sites 800 and 801 show breaks related to chert and radiolarite layers and are relatively vertical below. Above these chert units, pore waters are similar to modern seawater but below, they are between -10 per mil and -5.5 per mil. These values could represent little modified pre-Miocene seawater values, which were D-depleted because of the absence of polar caps, and were preserved from diffusive exchange with modern seawater by the relatively impermeable overlying chert layers. At Site 802, dD values of the pore waters show a decrease in the Miocene tuffs from 0 per mil values at the top to -8 per mil at 250 mbsf. Below, dD values are relatively uniform at about -8ë. Miocene tuffs are undergoing low water/rock alteration. A positive covariation of dD and Cl content of pore water in the tuffs suggests that the increase of dD values could result from secondary smectite formation. Low diffusive exchange coupled with D enrichment due to alteration of preglacial waters could explain the observed profile.

Multi-scale study of hydrogen isotopes structural properties in solid phase in the context of inertial fusion target manufacturing

Designing the ignition and high-gain targets for inertial confinement fusion (ICF) requires a condensed uniform layer of the hydrogen fuel on the inner surface of a spherical polymer shell. The fuel layers have to be highly uniform in thickness and roughness.

Flammability conditions for ultra-lean hydrogen premixed combustion based on flame-ball analyses

It has been reasoned that the structures of strongly cellular flames in very lean mixtures approach an array of flame balls, each burning as if it were isolated, thereby indicating a connection between the critical conditions required for existence of steady flame balls and those necessary for occurrence of self-sustained premixed combustion. This is the starting assumption of the present study, in which structures of near-limit steady sphericosym-metrical flame balls are investigated with the objective of providing analytic expressions for critical combustion conditions in ultra-lean hydrogen-oxygen mixtures diluted with N2 and water vapor. If attention were restricted to planar premixed flames, then the lean-limit mole fraction of H2 would be found to be roughly ten percent, more than twice the observed flammability limits, thereby emphasizing the relevance of the flame-ball phenomena. Numerical integrations using detailed models for chemistry and radiation show that a onestep chemical-kinetic reduced mechanism based on steady-state assumptions for all chemical intermediates, together with a simple, optically thin approximation for water-vapor radiation, can be used to compute near-limit fuel-lean flame balls with excellent accuracy. The previously developed one-step reaction rate includes a crossover temperature that determines in the first approximation a chemical-kinetic lean limit below which combustión cannot occur, with critical conditions achieved when the diffusion-controlled radiation-free peak temperature, computed with account taken of hydrogen Soret diffusion, is equal to the crossover temperature. First-order corrections are found by activation-energy asymptotics in a solution that involves a near-field radiation-free zone surrounding a spherical flame sheet, together with a far-field radiation-conduction balance for the temperature profile. Different scalings are found depending on whether or not the surrounding atmosphere contains wáter vapor, leading to different analytic expressions for the critical conditions for flame-ball existence, which give results in very good agreement with those obtained by detailed numerical computations.

Estudio de la movilidad que presenta el diésel en un suelo contaminado empleando surfactantes

La contaminación de suelos con hidrocarburos de petróleo en México es un problema que se ha vuelto muy común en nuestros días, debido principalmente a derrames, así como a las actividades propias de la industria petrolera. Algunos suelos contaminados, principalmente en el sureste de México, contienen concentraciones de hidrocarburos hasta de 450,000 mg/kg. Por dichas razones, una de las preocupaciones de las autoridades ambientales es el desarrollo de tecnologías eficientes y económicamente factibles que permitan la eliminación de este tipo de contaminantes. El saneamiento del sitio se puede lograr a través de diversos procedimientos, como son la aplicación de métodos físicos, químicos y biológicos (o combinaciones de ellas). La elección de un método depende de la naturaleza del contaminante, su estado físico, concentración, tipo de suelo, espacio físico disponible, tiempo destinado para su tratamiento, así como de los recursos económicos disponibles. Previa a la aplicación de la tecnología es necesario la realización de un diagnóstico de la contaminación del suelo, con el fin de conocer el tipo, concentración y distribución de los contaminantes presentes, así como el volumen de suelo a tratar, las condiciones climáticas de la zona, y características físicas del lugar (vías de acceso y servicios, entre otros). En la presente tesis, el empleo de surfactantes, se ha propuesto como una técnica para incrementar la movilidad de contaminantes orgánicos hidrofóbicos (HOCs) como hidrocarburos totales del petróleo (HTPs), bifenilos policlorados (PCBs), Benceno, Tolueno, Xilenos, explosivos, clorofenoles, pesticidas, entre otros, y así facilitar su degradación. Los surfactantes debido a que reducen la tensión superficial del agua, son moléculas formadas por grupos polares hidrofílicos y largas cadenas carbonadas hidrofóbicas. Sus grupos polares forman puentes hidrógeno con las moléculas de agua, mientras que las cadenas carbonadas se asocian a los hidrocarburos debido a interacciones hidrofóbicas que estos presentan. En soluciones acuosas, los surfactantes forman estructuras esféricas organizadas llamadas micelas. La solubilización de los contaminantes se lleva a cabo solamente cuando se forma la fase micelar, la cual se obtiene cuando la concentración del surfactante es superior a la concentración micelar crítica (CMC), es decir, arriba de la concentración de la cual el monómero se comienza a auto-agregar. La eficiencia de desorción de diésel por un surfactante depende de su naturaleza, de la dosis empleada, de la hidrofobicidad del contaminante, de la interacción surfactante-suelo y del tiempo de contacto surfactante-suelo. Sin embargo, la mejor eficiencia de desorción no está siempre relacionada con la mejor eficiencia de movilidad o solubilidad, debido principalmente a que el empleo de una alta concentración de surfactante puede inhibir la movilización. De acuerdo con información proporcionada por la Procuraduría Federal de Protección al Ambiente (PROFEPA), a la fecha no se ha llevado a cabo en México ninguna restauración de sitios específicamente contaminados con diésel, la técnica de lavado de suelos. Por lo anterior existe la necesidad de emplear la técnica de lavado de suelos ex situ. Específicamente en el suelo extraído de la ex refinería 18 de marzo ubicada en el Distrito Federal México y empleando una solución de surfactantes con agua desionizada, la cual consiste ponerlos en contacto con el suelo contaminado con diésel por medio de columnas de lavado cilíndricas, para lograr la remoción del contaminante. Se emplearon como surfactantes el lauril sulfato de sodio, lauril éter sulfato de sodio y Glucopon AV-100 a diferentes concentraciones de 0.5 a 4.0 [g/L], lográndose obtener una eficiencia del 80 % con este último surfactante. El lavado de suelos contaminados con diésel empleado surfactantes, es una tecnología que requiere que se profundice en el estudio de algunas variables como son el tipo de surfactante, concentración, tiempo de lavado, fenómenos de difusión, desorción, propiedades termodinámicas, entre otros. Los cuales determinarán el éxito o fracaso de la técnica empleada. Nowadays, soil pollution with oil in Mexico is a very common issue due mainly to both oil spill and oil activities. For example, mainly in the southeast area of Mexico, polluted soil contains high concentrations of hydrocarbons, up to 450,000 mg/kg. For these reasons, enviromental authorities have the concern in developing economically feasible and efficient technology that allow the elimination of these type of contaminants. The sanitation in sites can be achieved through several procedures such as physical, chemical and biological methods (or a combination among them). The choice of a method depends on the nature and physical state of the contaminant, the concentration, type of soil, physical space available, time consumption and financial resources. Before any technological application, a diagnostic of the polluted soil is necessary in order to know the type, concentration and distribution of contaminants as well as the soil volume, climatic conditions and physical features of the place (access routes and services, among others). In this thesis, surfactants has been proposed as a technique to increase the mobility of hydrophobic-organic contaminants (HOCs), e.g. total hydrocarbons of petroleum, polychlorinated biphenyls, benzene, toluene, xylenes, explosives, chlorophenols, pesticides, among others, and, hence, to facilitate degradation. Since surfactants reduce the water surface tension, they are molecules comprised of hydrophilic polar groups and long-hydrophobic carbon chains. Surfactant’s polar groups form hydrogen bonding with water molecules while carbon chains, i.e. hydrocarbon chains, have hydrophobic interactios. In aqueous solutions, surfactants form self-organised spherical structures called micelles. The solubilisation of contaminants is carried out only when the micellar phase is formed. This is obtained when the surfactant concentration is higher than the crítical micelle concentration (CMC), i.e. above the concentration where the surfactant monomer begins to self-aggregate. The diesel efficiency desorption by surfactants depends on their nature, the dose use, the contaminant hydrophobicity, the surfactant-soil interaction and the contact time with surfactant soil. However, the best desorption is not always related with the best either mobility or solubility efficiency since high concentration of surfactant can inhibit mobilisation. According to information of the Federal Bureau of Environmental Protection (PROFEPA), up today, there is not any restauration of diesel-polluted sites using the washing-soil technique. Due to the above, there exist the necessity of employing the waching-soil technique ex situ. More specifically, a sample soil from the oil-refinery of “18 de marzo” in Mexico city was extracted and a surfactant solution with deionised water was put in contact with the diesel contaminated soil by means of cylindrical waching columns in order to remove the contaminant. The surfactants employed in this work were sodium lauryl sulfate, sodium lauryl ether sulfate and Glucopon AV-100 at different concentrations of 0.5 to 4 [g/L], obtaining a efficiency of 80 % with this last surfactant. The washing of diesel-polluted soil using surfactants is a technology which requires a deeper study of some variables such as the type of surfactant, concentration, washing time, difusión phenomena, desorption, thermodynamic properties, among others. These parameters determine the succes or failure of the employed technique.