Raman and infrared spectra of dimethyl ether 13C-isotopologue (CH3O13CH3) from a CCSD(T) potential energy surface

So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm−1 of the infrared spectrum and around 400 cm−1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied.

Modelización del registro y proceso de datos espectrales, referidos a superficies líticas, en un ámbito arqueológico.

La determinación del origen de un material utilizado por el hombre en la prehistoria es de suma importancia en el ámbito de la arqueología. En los últimos años, los estudios de procedencia han utilizado técnicas que suelen ser muy precisas pero con el inconveniente de ser metodologías de carácter destructivo. El fenómeno de la minería a gran escala es una de las características que acompaña al Neolítico, de ahí que la revolución correspondiente a este periodo sea una de las etapas más importantes para la humanidad. El yacimiento arqueológico de Casa Montero es una mina de sílex neolítica ubicada en la Península Ibérica, de gran importancia por su antigüedad y su escala productiva. Este sitio arqueológico corresponde a una cantera de explotación de rocas silícicas desarrollada en el periodo neolítico en la que solamente se han encontrado los desechos de la extracción minera, lo cual incrementa la variabilidad de las muestras analizadas, de las que se desconoce su contexto económico, social y cultural. Es de gran interés arqueológico saber por qué esos grupos neolíticos explotaban de forma tan intensiva determinados tipos de material y cuál era el destino de la cadena productiva del sílex. Además, por ser una excavación de rescate, que ha tenido que procesar varias toneladas de material, en un tiempo relativamente corto, requiere de métodos expeditivos de clasificación y manejo de dicho material. Sin embargo,la implementación de cualquier método de clasificación debe evitar la alteración o modificación de la muestra,ya que,estudios previos sobre caracterización de rocas silícicas tienen el inconveniente de alterar parcialmente el objeto de estudio. Por lo que el objetivo de esta investigación fue la modelización del registro y procesamiento de datos espectrales adquiridos de rocas silícicas del yacimiento arqueológico de Casa Montero. Se implementó la metodología para el registro y procesamiento de datos espectrales de materiales líticos dentro del contexto arqueológico. Lo anterior se ha conseguido con la aplicación de modelos de análisis espectral, algoritmos de suavizado de firmas espectrales, reducción de la dimensionalidad de las características y la aplicación de métodos de clasificación, tanto de carácter vectorial como raster. Para la mayoría de los procedimientos se ha desarrollado una aplicación informática validada tanto por los propios resultados obtenidos como comparativamente con otras aplicaciones. Los ensayos de evaluación de la metodología propuesta han permitido comprobar la eficacia de los métodos. Por lo que se concluye que la metodología propuesta no solo es útil para materiales silícicos, sino que se puede generalizar en aquellos procesos donde la caracterización espectral puede ser relevante para la clasificación de materiales que no deban ser alterados, además, permite aplicarla a gran escala, dado que los costes de ejecución son mínimos si se comparan con los de métodos convencionales. Así mismo, es de destacar que los métodos propuestos, representan la variabilidad del material y permiten relacionarla con el estado del yacimiento, según su contenido respecto de las tipologías de la cadena operativa. ABSTRACT: The determination of the origin of a material used by man in prehistory is very important in the field of archaeology. In recent years the provenance studies have used techniques that tend to be very precise but with the drawback of being destructive methodologies. The phenomenon of mining on a large scale is a feature that accompanies the Neolithic period; the Neolithic revolution is one of the most important periods of humanity. The archaeological site of Casa Montero is a Neolithic flint mine located in the Iberian Peninsula of great importance for its antiquity and its scale. This archaeological site corresponds to a quarry exploitation of silicic rocks developed in the Neolithic period, in which only found debris from mining, which increases the variability of the samples analyzed, including their economic, social and cultural context is unknown. It is of great archaeological interest to know why these Neolithic groups exploited as intensive certain types of material and what the final destination of flint was in the productive chain. In addition, being an excavation of rescue that had to process several tons of material in a relatively short time requires expeditious methods of classification and handling of the material. However, the implementation of any method of classification should avoid the alteration or modification of the sample, since previous studies on characterization of silicic rocks have the disadvantage of destroying or partially modify the object of study. So the objective of this research wasthe modeling of the registration and processing of acquired spectral data of silicic rocks of the archaeological site of Casa Montero. The methodology implemented for modeling the registration and processing of existing spectral data of lithic materials within the archaeological context, was presented as an alternative to the conventional classification methods (methods destructive and expensive) or subjective methods that depend on the experience of the expert. The above has been achieved with the implementation of spectral analysis models, smoothing of spectral signatures and the dimensionality reduction algorithms. Trials of validation of the proposed methodology allowed testing the effectiveness of the methods in what refers to the spectral characterization of siliceous materials of Casa Montero. Is remarkable the algorithmic contribution of the signal filtering, improve of quality and reduction of the dimensionality, as well the proposal of using raster structures for efficient storage and analysis of spectral information. For which it is concluded that the proposed methodology is not only useful for siliceous materials, but it can be generalized in those processes where spectral characterization may be relevant to the classification of materials that must not be altered, also allows to apply it on a large scale, given that the implementation costs are minimal when compared with conventional methods.

Caracterización de variables geoespaciales mediante teledetección multiespectral y su integración en la modelización hidráulica de la cuenca del río Tinguiririca (Chile)

Este proyecto tiene como objetivo ampliar, mediante la caracterización espectral y multitemporal por técnicas de teledetección y medidas in situ, el estudio del corredor fluvial para el río Tinguiririca en Chile. Consiste en estudiar la cobertura del terreno, evaluar su dinámica de cambio e identificar zonas de acumulación de materiales de alteración hidrotermal arcillosos y óxidos de hierro, presentes en la cuenca durante las últimas tres décadas que puedan explicar su evolución temporal. Se pretenden obtener nuevas variables geoespaciales que ayuden a comprender las posibles causas de variación del cauce, elaborando cartografía para una posterior fase de investigación mediante modelización hidráulica que vaya dirigida a paliar el impacto de las riadas periódicas. Para ello, se han empleado, tratado y explotado imágenes de los sensores remotos TM, ETM+, OLI y TIRS tomadas en un período comprendido entre 1993 y 2014, que se han contrastado con perfiles batimétricos, datos GPS, supervisión y muestreo tomados sobre el terreno. Se ha realizado así mismo, un estudio prospectivo de caso sobre cómo afectarían las variables obtenidas por teledetección a la modelización hidráulica, en particular, la rugosidad, proponiendo un marco metodológico global de integración de las tres técnicas: sistemas de información geográfica, teledetección y modelización hidráulica. ABSTRACT This project aims to develop the study of Tinguiririca River corridor in Chile, through spectral characterization and multitemporal remote sensing and other measurements. This involves studying the land cover, its dynamic changes and identifies clayey materials and iron oxides accumulations of hydrothermal alteration, present in the basin during the last three decades to explain their evolution. It aims to obtain new geospatial variables in order to understand the possible causes of channel variation, developing mapping to a later research stage using hydraulic modeling so as to mitigate the impact of periodic floods. In this way, it has used processed and exploited images of TM, ETM +, OLI and TIRS remote sensing, taken in a period between 1993 and 2014 which it has been compared with bathymetric profiles, GPS, monitoring and sampling data collected in the field . It has done a prospective study about the variables obtained condition on hydraulic modeling, roughness in particular, proposing IX a complete methodological framework about the integration of the three techniques: geographic information systems, remote sensing and modeling hydraulics

Spectral-analysis-surface-waves-method in ground characterization

The prediction of train induced vibration levels in structures close to railway tracks before track construction starts is important in order to avoid having to implement costly mitigation measures afterwards. The used models require an accurate characterization of the propagation medium i.e. the soil layers. To this end the spectral analysis of surface waves (SASW) method has been chosen among the active surface waves techniques available. As dynamic source a modal sledge hammer has been used. The generated vibrations have been measured at known offsets by means of several accelerometers. There are many parameters involved in estimating the experimental dispersion curve and, later on, thickness and propagation velocities of the different layers. Tests have been carried out at the Segovia railway station. Its main building covers some of the railway tracks and vibration problems in the building should be avoided. In the paper these tests as well as the influence of several parameters on the estimated soil profile will be detailed.

Advances in the modeling, characterization and reliability of concentrator multijunction solar cells

Los sistemas de concentración fotovoltaica (CPV) parecen ser una de las vías más prometedoras para generar electricidad a gran escala a precios competitivos. La investigación actual se centra en aumentar la eficiencia y la concentración de los sistemas para abaratar costes. Al mismo tiempo se investiga sobre la fiabilidad de los diferentes componentes que integran un sistema de concentración, ya que para que los sistemas de concentración sean competitivos es necesario que tengan una fiabilidad al menos similar a los sistemas basados en células de silicio. En la presente tesis doctoral se ha llevado a cabo el estudio de aspectos avanzados de células solares multi-unión diseñadas para trabajar a concentraciones ultra-altas. Para ello, se ha desarrollado un modelo circuital tridimensional distribuido con el que simular el comportamiento de las células solares triple-unión bajo distintas condiciones de funcionamiento, así mismo se ha realizado una caracterización avanzada de este tipo de células para comprender mejor su modo de operación y así poder contribuir a mejorar su eficiencia. Finalmente, se han llevado a cabo ensayos de vida acelerados en células multiunión comerciales para conocer la fiabilidad de este tipo de células solares. Para la simulación de células solares triple-unión se ha desarrollado en la presente tesis doctoral un modelo circuital tridimensinal distribuido el cuál integra una descripción completa de la unión túnel. De este modo, con el modelo desarrollado, hemos podido simular perfiles de luz sobre la célula solar que hacen que la densidad de corriente fotogenerada sea mayor a la densidad de corriente pico de la unión túnel. El modelo desarrollado también contempla la distribución lateral de corriente en las capas semiconductoras que componen y rodean la unión túnel. Por tanto, se ha podido simular y analizar el efecto que tiene sobre el funcionamiento de la célula solar que los concentradores ópticos produzcan perfiles de luz desuniformes, tanto en nivel de irradiancia como en el contenido espectral de la luz (aberración cromática). Con el objetivo de determinar cuáles son los mecanismos de recombinación que están limitando el funcionamiento de cada subcélula que integra una triple-unión, y así intentar reducirlos, se ha llevado a cabo la caracterización eléctrica de células solares monouni ón idénticas a las subcelulas de una triple-unión. También se ha determinado la curva corriente-tensión en oscuridad de las subcélulas de GaInP y GaAs de una célula dobleunión mediante la utilización de un teorema de reciprocidad electro-óptico. Finalmente, se ha analizado el impacto de los diferentes mecanismos de recombinación en el funcionamiento de la célula solar triple-unión en concentración. Por último, para determinar la fiabilidad de este tipo de células, se ha llevado a cabo un ensayo de vida acelerada en temperatura en células solares triple-unión comerciales. En la presente tesis doctoral se describe el diseño del ensayo, el progreso del mismo y los datos obtenidos tras el análisis de los resultados preliminares. Abstract Concentrator photovoltaic systems (CPV) seem to be one of the most promising ways to generate electricity at competitive prices. Nowadays, the research is focused on increasing the efficiency and the concentration of the systems in order to reduce costs. At the same time, another important area of research is the study of the reliability of the different components which make up a CPV system. In fact, in order for a CPV to be cost-effective, it should have a warranty at least similar to that of the systems based on Si solar cells. In the present thesis, we will study in depth the behavior of multijunction solar cells under ultra-high concentration. With this purpose in mind, a three-dimensional circuital distributed model which is able to simulate the behavior of triple-junction solar cells under different working conditions has been developed. Also, an advanced characterization of these solar cells has been carried out in order to better understand their behavior and thus contribute to improving efficiency. Finally, accelerated life tests have been carried out on commercial lattice-matched triple-junction solar cells in order to determine their reliability. In order to simulate triple-junction solar cells, a 3D circuital distributed model which integrates a full description of the tunnel junction has been developed. We have analyzed the behavior of the multijunction solar cell under light profiles which cause the current density photo-generated in the solar cell to be higher than the tunnel junction’s peak current density. The advanced model developed also takes into account the lateral current spreading through the semiconductor layers which constitute and surround the tunnel junction. Therefore, the effects of non-uniform light profiles, in both irradiance and the spectral content produced by the concentrators on the solar cell, have been simulated and analyzed. In order to determine which recombination mechanisms are limiting the behavior of each subcell in a triple-junction stack, and to try to reduce them when possible, an electrical characterization of single-junction solar cells that resemble the subcells in a triplejunction stack has been carried out. Also, the dark I-V curves of the GaInP and GaAs subcells in a dual-junction solar cell have been determined by using an electro-optical reciprocity theorem. Finally, the impact of the different recombination mechanisms on the behavior of the triple-junction solar cell under concentration has been analyzed. In order to determine the reliability of these solar cells, a temperature accelerated life test has been carried out on commercial triple-junction solar cells. In the present thesis, the design and the evolution of the test, as well as the data obtained from the analysis of the preliminary results, are presented.

Seismic Hazard and Ground Motion Characterization at the Itoiz Dam (Northern Spain).

This paper presents a new hazard-consistent ground motion characterization of the Itoiz dam site, located in Northern Spain. Firstly, we propose a methodology with different approximation levels to the expected ground motion at the dam site. Secondly, we apply this methodology taking into account the particular characteristics of the site and of the dam. Hazard calculations were performed following the Probabilistic Seismic Hazard Assessment method using a logic tree, which accounts for different seismic source zonings and different ground-motion attenuation relationships. The study was done in terms of peak ground acceleration and several spectral accelerations of periods coinciding with the fundamental vibration periods of the dam. In order to estimate these ground motions we consider two different dam conditions: when the dam is empty (T = 0.1 s) and when it is filled with water to its maximum capacity (T = 0.22 s). Additionally, seismic hazard analysis is done for two return periods: 975 years, related to the project earthquake, and 4,975 years, identified with an extreme event. Soil conditions were also taken into account at the site of the dam. Through the proposed methodology we deal with different forms of characterizing ground motion at the study site. In a first step, we obtain the uniform hazard response spectra for the two return periods. In a second step, a disaggregation analysis is done in order to obtain the controlling earthquakes that can affect the dam. Subsequently, we characterize the ground motion at the dam site in terms of specific response spectra for target motions defined by the expected values SA (T) of T = 0.1 and 0.22 s for the return periods of 975 and 4,975 years, respectively. Finally, synthetic acceleration time histories for earthquake events matching the controlling parameters are generated using the discrete wave-number method and subsequently analyzed. Because of the short relative distances between the controlling earthquakes and the dam site we considered finite sources in these computations. We conclude that directivity effects should be taken into account as an important variable in this kind of studies for ground motion characteristics.

Characterization of an 241AmBe neutron irradiation facility by different spectrometric techniques

An automated panoramic irradiator with a 3 Ci 241Am-Be neutron source is installed in a bunker-type large room at the Universidad Politécnica de Madrid (UPM). It was recently modified and a neutron spectrometry campaign was organized to characterize the neutron fields in different measurement points along the irradiation bench. Four research groups working with different Bonner Sphere Spectrometers (BSS) and using different spectral unfolding codes took part to this exercise. INFN-LNF used a BSS formed by 9 spheres plus bare detector, with cylindrical, almost point like, 6LiI(Eu) scintillator (4 mm x 4 mm, from Ludlum); UAZ-UPM employed a similar system but with only 6 spheres plus bare detector; UAB worked with a 3He filled proportional counter at 8kPa filling pressure, cylindrical 9 mm x 10 mm (05NH1 from Eurisys) with 11 spheres configuration; and CIEMAT used 12 spheres with an spherical 3He SP9 counter (Centronic Ltd., UK) with very high sensitivity due to the large diameter (3.2 cm) and the filling pressure of the order of 228 kPa. Each group applied a different spectral unfolding method: INFN and UAB worked with FRUIT ver. 3.0 with their own response matrixes; UAZ-UPM used the BUNKIUT unfolding code with the response matrix UTA4 and CIEMAT employed the GRAVEL-MAXED-IQU package with their own response matrix. The paper shows the main results obtained in terms of neutron spectra at fixed distances from the source as well as total neutron fluence rate and ambient dose equivalent rate H*(10) determined from the spectra. The latter are compared with the readings of a common active survey-meter (LB 6411). The small differences in the results of the various groups are discussed.

Surface Impedance Characterization for UTD Based Solution with IBC for Surface Fields on a Dielectric-Coated PEC Circular Cylinder

A novel formulation for the surface impedance characterization is introduced for the canonical problem of surface fields on a perfect electric conductor (PEC) circular cylinder with a dielectric coating due to a electric current source using the Uniform Theory of Diffraction (UTD) with an Impedance Boundary Condition (IBC). The approach is based on a TE/TM assumption of the surface fields from the original problem. Where this surface impedance fails, an optimization is performed to minimize the error in the SD Green?s function between the original problem and the equivalent one with the IBC. This new approach requires small changes in the available UTD based solution with IBC to include the geodesic ray angle and length dependence in the surface impedance formulas. This asymptotic method, accurate for large separations between source and observer points, in combination with spectral domain (SD) Green?s functions for multidielectric coatings leads to a new hybrid SD-UTD with IBC to calculate mutual coupling among microstrip patches on a multilayer dielectric-coated PEC circular cylinder. Results are compared with the eigenfunction solution in SD, where a very good agreement is met.

Surface Impedance Characterization for Mutual Coupling Calculation of Patches on a Dielectric-Coated PEC Circular Cylinder

A novel formulation for the surface impedance characterization is introduced for the canonical problem of surface fields on a perfect electric conductor (PEC) circular cylinder with a dielectric coating due to a electric current source using the Uniform Theory of Diffraction (UTD) with an Impedance Boundary Condition (IBC). The approach is based on a TE/TM assumption of the surface fields from the original problem. Where this surface impedance fails, an optimization is performed to minimize the error in the SD Green?s function between the original problem and the equivalent one with the IBC. This asymptotic method, accurate for large separations between source and observer points, in combination with spectral domain (SD) Green?s functions for multidielectric coatings leads to a new hybrid SD-UTD with IBC to calculate mutual coupling among microstrip patches on a multilayer dielectric-coated PEC circular cylinder. Results are compared with the eigenfunction solution in SD, where a very good agreement is met.

Analysis of spontaneous MEG activity in mild cognitive impairment and Alzheimer's disease using spectral entropies and statistical complexity measures

Alzheimer's disease (AD) is the most common cause of dementia. Over the last few years, a considerable effort has been devoted to exploring new biomarkers. Nevertheless, a better understanding of brain dynamics is still required to optimize therapeutic strategies. In this regard, the characterization of mild cognitive impairment (MCI) is crucial, due to the high conversion rate from MCI to AD. However, only a few studies have focused on the analysis of magnetoencephalographic (MEG) rhythms to characterize AD and MCI. In this study, we assess the ability of several parameters derived from information theory to describe spontaneous MEG activity from 36 AD patients, 18 MCI subjects and 26 controls. Three entropies (Shannon, Tsallis and Rényi entropies), one disequilibrium measure (based on Euclidean distance ED) and three statistical complexities (based on Lopez Ruiz–Mancini–Calbet complexity LMC) were used to estimate the irregularity and statistical complexity of MEG activity. Statistically significant differences between AD patients and controls were obtained with all parameters (p < 0.01). In addition, statistically significant differences between MCI subjects and controls were achieved by ED and LMC (p < 0.05). In order to assess the diagnostic ability of the parameters, a linear discriminant analysis with a leave-one-out cross-validation procedure was applied. The accuracies reached 83.9% and 65.9% to discriminate AD and MCI subjects from controls, respectively. Our findings suggest that MCI subjects exhibit an intermediate pattern of abnormalities between normal aging and AD. Furthermore, the proposed parameters provide a new description of brain dynamics in AD and MCI.

Non-destructive optical characterization of fruits in the red and near infrared.

Increasing attention is being paid to the possible development of non-invasive tests for the assessment of the quality of Fruits. We propose a novel non-destructive method for the measurement of the internal optical properties of fruits and vegetables by means of lime-resolved reflectance spectroscopy in the visible and NIR range. A Fully automated instrumentation for time-resolved reflectance measurements was developed. It is based on mode-locked laser sources and electronics for time-correlated single photon counting, and provides a time-resolution of 120-160 ps. The system was used to probe the optical properties of several species and varieties of Fruits and vegetables in the red and NIR range (650-1000 nm). In most Fruits, the absorption line shape is dominated by the absorption peak of water, centred around 970 nm. Generally, the absorption spectra also show the spectral features typical of chlorophyll, with maximum at 675 nm. In particular, for what concerns apples, variations in peak intensity are observed depending on the variety, the degree of ripeness as well as the position on the apple. For all the species and varieties considered, the transport scattering coefficient decreases progressively upon increasing the wavelength.

In-situ and Ex-situ characterization of III-V semiconductor materials and solar cells upon 10 MEV proton irradiation

In this work we present the results and analysis of a 10 MeV proton irradiation experiment performed on III-V semiconductor materials and solar cells. A set of representative devices including lattice-matched InGaP/GaInAs/Ge triple junction solar cells and single junction GaAs and InGaP component solar cells and a Ge diode were irradiated for different doses. The devices were studied in-situ before and after each exposure at dark and 1 sun AM0 illumination conditions, using a solar simulator connected to the irradiation chamber through a borosilicate glass window. Ex-situ characterization techniques included dark and 1 sun AM0 illumination I-V measurements. Furthermore, numerical simulation of the devices using D-AMPS-1D code together with calculations based on the TRIM software were performed in order to gain physical insight on the experimental results. The experiment also included the proton irradiation of an unprocessed Ge solar cell structure as well as the irradiation of a bare Ge(100) substrate. Ex-situ material characterization, after radioactive deactivation of the samples, includes Raman spectroscopy and spectral reflectivity.

Horizontal to vertical spectral ratio measurements in Port-au-Prince (Haiti) area damaged by the 2010 Haiti earthquake

In order to evaluate ground shaking characteristics due to surface soil layers in the urban area of Port-au-Prince, short-period ambient noise observation has been performed approximately in a 500x500m grid. The HVSR method was applied to this set of 36 ambient noise measurement points to determine a distribution map of soil predominant periods. This map reveals a general increasing trend in the period values, from the Miocene conglomerates in the northern and southern parts of the town to the central and western zones formed of Pleistocene and Holocene alluvial deposits respectively, where the shallow geological materials that cover the basement increase in thickness. Shorter predominant periods (less than 0.3 s) were found in mountainous and neighbouring zones, where the thickness of sediments is smaller whereas longer periods (greater than 0.5 s) appear in Holocene alluvial fans, where the thickness of sediments is larger. The shallow shear-wave velocity structure have been estimated by means of inversion of Rayleigh wave dispersion data obtained from vertical-component array records of ambient noise. The measurements were carried out at one open space located in Holocene alluvial deposits, using 3 regular pentagonal arrays with 5, 10 and 20m respectively. Reliable dispersion curves were retrieved for frequencies between 4.0 and 14 Hz, with phase velocity values ranging from 420m/s down to 270 m/s. Finally, the average shear-wave velocity of the upper 30 m (VS30) was inverted for characterization of this geological unit.

VIS/NIR spectral signature for the identification of peanut contamination of powder foods

Visible-near infrared reflectance spectra are proposed for the characterization of IRMM 481 peanuts variety in comparison to powder food materials: wheat flour, milk and cocoa. Multidimensional analysis of reflectance spectra of powder samples shows a specific NIR band centred at 1200 nm that identifies peanut compared to the rest of food ingredients, regardless compaction level and temperature. Spectral range of 400-1000 nm is not robust for identification of blanched peanut. The visible range has shown to be reliable for the identification of pre-treatment and processing of unknown commercial peanut samples. A spectral index is proposed based on the combination of three wavelengths around 1200 nm that is 100% robust against pre-treatment (raw or blanched) and roasting (various temperatures and treatment duration).