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Galactic archaeology in the 21st century : unveiling accretion in the MW disc
(Universidad Andrés Bello, 2022) Tronrud, Thorold; Tissera, Patricia; Gómez, Facundo A.; Gómez, Matías; Bignone, Lucas; Facultad de Ciencias Exactas
The evolution of large galaxies such as the Milky Way (MW) in Λ Cold Dark Matter (ΛCDM) cosmology is driven by interactions with other galaxies. These interactions affect the structure of the galaxy in long-lasting ways, not only forming the stellar halo, and modifying the size and characteristics of the stellar disc, but also contributing gas that fuels star formation and depositing stars directly into the galaxy. This stellar debris, formed outside the galaxy in which they now reside (a.k.a. ex-situ), retain the chemical fingerprint of the environment in which they formed, leaving them distinct from the stars that were formed within the primary galaxy (a.k.a. in-situ). If these ex-situ stars are located beyond the disc, in the stellar halo, the distributions they occupy in space — based on the kinematics of their progenitor object — may be readily apparent as streams or great circles surrounding the primary galaxy. A population of ex-situ stars are also expected to reside in the stellar disc, even at high circularities. These stars have been found in simulations to be deposited by relatively few massive mergers, but finding them poses a challenge in this dense region. I propose a method, based on training and utilizing neural networks, to classify disc stars as in- or ex-situ based on their chemical parameters. The use of this method is motivated by my research into the effects mergers and accretion have on the galactic stellar disc of a suite of simulated MW-like galaxies, in which I demonstrate that accretion events and accreted stars cause observable changes to calculated metallicity gradients, and can cause disagreements in correlations between observed parameters based on the ages of the stars being used. Galactic discs form inside-out, starting small and slowly expanding with new star formation at the outer edges. This imparts a natural negative age gradient. Stars that have been deposited onto the disc will not necessarily follow this age gradient, which is one of the primary drivers of the stellar disc’s metallicity gradient. These ex-situ stars drive several age-specific correlations between metallicity gradient and 𝑅 −1 eff and 𝜆 ★ gal that vanish entirely once these contaminants are removed. A chemistry-based method for flagging potentially-accreted stars will allow researchers to remove the bulk of these from their samples, which will allow them to examine the evolution of the galactic disc more finely. Furthermore, these flagged, ex-situ stars can be grouped by their characteristics, for attempts to discern early progenitors of the primary galaxy with significantly less noise from stars formed in-situ. I demonstrate that the Galactic Archaeology Neural Network (GANN) recovers usable fractions of nearly every contributor to the suite of simulated stellar discs. Thus, a catalogue of stars flagged by GANN will contain most of the merger information that is present in the stellar disc of a galaxy. Future applications of this method could aid in the discovery of many ancient remnants, and broaden our understanding of how our galaxy formed.
Description of the optical and molecular properties in lanthanide macrocyclic complexes using quantum chemical relativistic methods
(Universidad Andrés Bello, 2015) Rabanal León, Walter A; Arratia Pérez, Ramiro; Facultad de Ciencias Exactas
The lanthanides or most commonly known as .. rare earths" have attracted the interest of thc scic11tific comrnunity i11 thc last 30 ycars, duc to their uniquc and appealing characteristics. Probably, one of the most interesting is their f-f inherent spectroscopic properties in thc nea.r infra-red rcgion of the spectra prescnting charactcristic narrow "line-like" emission bands. Additionally, these f-f transitions are parity (and sornetimes also spin) forbidclen, rcsulting in vcry long livcd excited states. Unfortunately, as another consequence of the parity (Laporte) forbidden nature of the 4f transitions, the direct absorption of Ln(III) cations is quite poor, and they hence have very low molar absorption coefficients which limits their practical usage. For that reason, the use of molecular antennas, which absorbed highly effi.ciently the light and then promete a charge/energy transfer to the lanthanide center (populating their excited states), was proposed as a simple and useful way to sensitize and enhance the lanthanide luminescence. In this way, this doctoral dissertation entitled: "Description of the Optical and Molecular Properties in Lanthanide ::Ylacrocyclic Complexes Using Quantum Chemical Relativistic Methods", is a study based on the relativistic density functional and the wave-function theory of a series of poly-aza and poly-oxo lanthanide macrocyclic complexes, whose purpose is to characterize: i) the ground and excited states, ii) the lanthanide-macrocycle interaction, and iii) the nature of the main electronic transitions involved in optical applications. During the development of this work, we found interesting results on the characterization of the bond interaction, energetics and optical properties, that show the potential use of 1r-conjugated macrocyclic systems as molecular antennas which could sensitize the lanthanide luminescence throughout a charge transfer phcnomena, which is favoured by a dativc covalcnt intcraction betwccn thc macrocyclic ligand and the lanthanide center. Moreover, it was achieved an extensivc knowledge of thc clectronic structurc, cspecially the multi-coufigurational naturc of the ground and excited states, as a consequence of the low-lying character of the lanthanidc 4f-shcll ancl thc strong statc rnixiug possibility due to the low sy111rnetry and the spin-orbit coupling effect.
Caracterización teórica de catalizadores de Rutenio con potencial actividad en reacciones de metátesis
(Universidad Andrés Bello, 2014) Paredes Gil, Katerine; Jaque, Pablo
La metátesis de olefinas o reorganización de dobles enlaces C-C es una de las transformaciones químicas más utilizadas en las últimas dos décadas para la generación de numerosos compuestos dentro de la química fina, farmacológica, y ciencia de los materiales. Esta reacción ocurre a través de un catalizador metálico el cual está basado principalmente en complejos de rutenio tipo carbeno. Diversos estudios experimentales y computacionales han permitido comprender las características generales de este proceso, tal como es descrito en el Capítulo 1. Sin embargo, algunos aspectos de tipo electrónico, cinético y termodinámico podrían ser abordados desde el punto de vista computacional con el propósito de profundizar en el comportamiento químico de esta reacción. n esta dirección, un eje principal de discusión dentro de la metátesis de olefinas es la diferenciación de la reactividad de la 1 ra y 2dª generación de catalizadores de Grubbs. Múltiples estudios han abordado este tema a partir de los cambios energéticos que ocurren tanto en la reacción de disociación del ligando PR3 como en la interconversión de las especies catalíticas de 14e-. Sin embargo, el cambio en la reactividad de estos catalizadores en la etapa de formación del rutenaciclobutano no ha sido explorado, y es el tema central del Capítulo 4. Por otra parte, la identificación de las diferencias de los enlaces principales que participan en la etapa de iniciación, son descritas en el Capítulo 5. Ambos aspectos permitieron proponer que la mayor reactividad de la segunda generación en las reacciones de metátesis de olefinas debe entenderse como la suma de diferentes efectos dentro de la etapa de iniciación: cambios en la transferencia de carga, polarización y deslocalización electrónica, principalmente.
Optical and magnetic properties of organoactinide complexes an application of relativistic density functional theory
(Universidad Andrés Bello, 2012) Páez Hernández, Dayán
The discovery of slow magnetic relaxation in certain transition metal-oxo clusters revealed a new family of magnetic materia Is known as single-molecule magnets. Such molecules possess a high-spin ground state (with total spin S) for which spin-orbit coupling results in a zero-field splitting of the (2S + 1 )-fold degeneracy in a manner that creates a thermal relaxation barrier and gives rise to magnetic bistability at low temperature. Two major goals of research in this area are generating new molecules with larger relaxation barriers and understanding the quantum tunneling processes that can sho1tcut the ban-ier. The greater radial extension of the 5/ valence orbitals of actinides can potentially provide increased overlap with bridging ligand orbitals, thereby enhancing the concerted magnetic behavior between bridged metal centers within a single cluster unit. Researchers have confronted the intricacies of the magnetic exchange in a number of interesting ways, often with the goal of identifying and, to the extent possible, quantifying ferro- or antife1TOmagnetic exchange coupling. Understanding these exchange interactions not only is essential to the development of models for the basic electronic stmcture of the Velements but also may represent the key to producing the first actinide-based SMMs. In this work we present the theoretical investigation about the magnetic and optical properties for a group of organoactinide complexes. Our calculations reveal that the electron mobility (delocalization) and relativistic effect pa1ticularly spin-orbit coupling have a principal role for a good description of these properties in this kind of molecule. Also we propose sorne molecular models with desirable structural parameters when the optical and magnetic properties detennined should open the door to the design of new materials with potential technological applications.
Understanding quasar microlensing light curves in the context of large area surveys
(Universidad Andrés Bello, 2022) Neira, Favio; Anguita Timo; Facultad de Ciencias Exactas
The accretion disc around the super massive black hole (SMBH) of quasars, and active galactic nuclei (AGN) in general, is believed to be the central engine of the optical and UV continuum we observe. AGN and their host galaxy are tightly connected in their evolution, thus a detailed understanding of the accretion disc is required for a coherent picture of not only their evolution, but also of their environment and the large scale universe. However, due to how typically far away these objects are (z∼2), as well as how compact the are, we have not been able to directly resolve in detail its structure. One such method to indirectly probe these accretion discs relies on observing microlensing high magnification events (HME) in strongly lensed quasars. These kinds of studies usually consist of comparing observations with simulations in order to infer the properties of the accretion disc. However, these simulations are computationally expensive, especially due to the large range of parameters that needs to be explored. Furthermore, we expect to increase the number of lensed quasars from hundreds to the order of thousands. The few HME studies that have been been done are relegated to a few selected systems with specific parameters, this in part due to how few of them we had known and how hard it is to obtain suitable data for these studies. Because of this, preparation for the new systems is timely, however, there are not quantitative results that could allow us to prepare for this. In this thesis we provide a simulation framework from where microlensing light curves of lensed quasars can be generated and facilitate the study of high magnification events (HME). Motivated by the, yet to be fully unveiled, potential of HME at constraining the inner structure of quasar, the main goal of this work is to develop tools and methods to prepare for the forthcoming large area surveys. Specifically, we have built a tool that can generate simulated quasar microlensing light curves and serve as the foundation for qualitative and quantitative HME studies. To highlight the capabilities of i this tool to enable HME studies, we generated of the order of billions (109) simulated light curves and analyzed them to statistically study and understand the nature of HME. We studied three lensed quasar known to have microlensing, and show that, depending on their location on the sky, the lens and source redshift, and the caustic network density, the microlensing variability time scales may deviate from theoretical estimations. We estimate that 300 HME with Δm > 1 could potentially be observed by The Vera Rubin Observatory Legacy Survey of Space and Time (LSST) each year. We show that depending on the observing strategy adopted, in the best scenario only 20% of these events would be missed. We generated microlensing light curves for thousands of simulated lensed quasars. We estimate that about 55 HME with delta mag Δm > 0.3 could be observed each year in the southern (or northern) sky by most telescopes. We observe a broad range in frequency, duration and amplitude of these events. We show that this can be better understood by classifying these events by the parity of the image from which they were identified (i.e. minimum or saddle) and whether or not the center of the quasar accretion disc crosses a caustic during the event (caustic crossing). We assess the usefulness of the simulated lensed quasar images for HME studies and show that the top 20% can have 50% of the total expected number of events. The tool that has enabled these studies is publicly available at https://gerlumph.swin.edu. au/tools/lsst_generator/. There are many issues to address regarding HME studies, which the tool presented here could help to. We have shown how this tool can help push forward our understanding of HME, bringing us a step closer to developing the tools and methods that will allow us to make the most out of the forthcoming large area surveys.
Desarrollo e implementación de algoritmos híbridos para la exploración de la superficie de energía potencial en clusters atómicos y moleculares
(Universidad Andrés Bello, 2018) Yáñez Osses, Osvaldo Andrés; Tiznado, William; Garza Olguín, Jorge; Facultad de Ciencias Exactas
los cúmulos atómicos (clusters en este escrito) son entidades químicas con propiedades, físicas y químicas, particulares y dependientes de su tamaño. la química teórica, enmarcada en la mecánica cuántica y clásica, cumple un rol fundamental en el estudio de estos sistemas, ya que éstos se sintetizan mediante la atomización del material (a altas temperaturas) y las propiedades que se logran medir son en estado gaseoso. Por este motivo la forma práctica de asignación estructural se basa en medir la propiedad experimental con su contraparte teórica. Por ejemplo, se utilizan los espectros fotoelectrónicos para estas asignaciones, siendo éstos característicos de cada isómero (la estructura electrónica es muy dependiente de la estructura geométrica). la predicción conformacional de clusters atómicos tiene implicaciones relevantes en campos tan variados como el diseño de nanomateriales, nanobiomedicina, catálisis, entre otros, por lo tanto es necesario contar con un método confiable o una combinación de varios métodos para la exploración de las superficie de energía potencial (SEP) de clusters atómicos y moleculares. En consecuencia, la determinación de la estructura y de las propiedades físicas de un sistema molecular está íntimamente relacionada con el mínimo global en su SEP.
Compuestos metal-orgánicos con propiedades multifuncionales
(Universidad Andrés Bello, 2018) Baldo Hurtado, Bianca; Paredes García, Verónica; Facultad de Ciencias Exactas
RESUMEN El hecho que un compuesto metal-orgánico contenga tanto una parte orgánica como una inorgánica, hace que estos sistemas sean altamente modulables, desde la dimensionalidad de su estructura hasta las propiedades que se obtienen. Es así como durante el último tiempo, la química de coordinación ha estado enfocada en la síntesis de nuevos materiales basados en cationes 3d y 4f, enlazados a través de ligantes orgánicos con grupos funcionales de diferente naturaleza química, lo que hace posible encontrar en este tipo de materiales propiedades interesantes como luminiscencia, óptica no lineal y magnetismo, entre otras. Por otra paite, la síntesis de compuestos metal-orgánicos de mayor dimensionalidad se ha visto dominada por tiempos largos de reacción, además de la utilización de solventes orgánicos expuestos a condiciones de temperatura y presión mayores a las utilizadas en métodos de síntesis tradicionales. Sin embargo, en los últ imos años ha crecido el interés por el desarrollo de nuevas técnicas sintéticas con menores tiempos de reacción y más amigables con el medio ambiente, como son la mecanoquímica y sonoquímica.
Calculated optical properties of polypyridine complexes and its possible use in solar cells
(Universidad Andrés Bello, 2013) Schott Verdugo, Eduardo; Arratia Pérez, Ramiro; Facultad de Ciencias Exactas
A senes of polypyridyl complexes with tris-(2,2'-Bipyridine) and 2,2':6',2"-terpyridine substituted dyes and Ru(II) or Os(II) as central metal were studied. The influence on the variation of the substituents over the composition of the molecular orbitals, electronic transitions and reactivity of these compounds was studied. A good agreement with tbe previously reported experimental data, of the geometrical parameters and of the UV-Vis transitions, was found for the complexes which have previous experimental reports. In these theoretical calculations the -COOH anchor group to get attached to the semiconductor surface was included. Using the charge transfer analysis and the orbitals that are involved in the transitions, it was observed that the complexes that have electron-donor substituents might be more efficient to donate electrons when they are attached to a semiconductor surface than those complexes that have electron-acceptor substituents. Therefore the results suggest that these dyes with electron-donor substituents will give better yields in photocurrent generation. Also, the localization of the LUMO over the ligand that has the anchor will help to improve electron injections into the TiO2 nanoparticles. We propase here severa! not yet synthetized dyes, which could be used in this kind of devices, due to their interesting molecular properties. l
First-order Lagrangian of Lovelock gravity and applications
(Universidad Andrés Bello, 2022) Guilleminot Arellano, Pablo; Olea, Rodrigo; Merino, Nelson; Faraggi, Alberto; Miskovic, Olivera; Aros, Rodrigo; Corral, Cristóbal; Facultad de Ciencias Exactas
En este trabajo, se analizan, analíticamente, aspectos de evolución espacial en gravedad de Lovelock. Se muestra que la adición de términos de Myers a la acción elimina las derivadas de segundo orden respecto a la variable de evolución. Así, la conexión entre el problema de Dirichlet y Lagrangianos de primer orden es establecida. Luego, se exhibe como la transformada de Legendre de este último permite calcular directamente el Hamiltoniano del sistema para la misma variable de evolución. Con estos resultados, se analiza el comportamiento de cáscaras delgadas con masa en el contexto de gravedad de Lovelock. Para esto, se trabaja el principio variacional escrito en un set adaptado de coordenadas válido cerca de la cáscara. Se concluye que la cantidad que es discontínua en la cáscara es el momentum canónico. Finalmente se obtienen algunas expresiones explicitas para configuraciones con simetría esférica.
Desarrollo e implementación de métodos de cómputo para densidades de estados, usando ensambles generalizados
(Universidad Andrés Bello, 2022) Moreno Muñoz, Felipe Eduardo; Peralta, Joaquín; Davis, Sergio; Faraggi, Alberto; Gutiérrez, Gonzalo; Molina, Francisco; Poblete, Simón; Facultad de Ciencias Exactas
El presente trabajo se enfoca en el desarrollo e implementación de algoritmos de simulación que permitan calcular la Densidad de Estados (DOS) de sistemas de muchas partículas interactuantes usando ensambles generalizados. Métodos para obtener las propiedades de un sistema que se basan en el uso de ensambles canónicos o microcanónicos—como el popular algoritmo de Metropolis—se han usado durante ya un largo tiempo. Sin embargo, el empleo de ensambles generalizados muestra ser una alternativa que permite generar curvas más suaves con menor número de simulaciones, además de evitar ciertos problemas típicos de esos métodos como el tener dificultades para muestrear correctamente sistemas con muchos mínimos locales. En este trabajo se presenta una implementación flexible y modular del algoritmo de Wang–Landau, además de un novedoso algoritmo basado en un método Bayesiano para el cálculo directo de la DOS, los cuales puede ser usados para obtener las propiedades termodinámicas de un sistema con una superficie de energía potencial compleja. Nuestros resultados muestran que los algoritmos son capaces de calcular la DOS con razonable precisión. Hemos estudiado, como aplicación de los métodos anteriormente mencionados, las propiedades termodinámicas de un modelo de Potts de 3 estados modificado, en el contexto de la aproximación de “lattice gas” para partículas cargadas confinadas en un volumen.
DFT study of the optical properties and substituent effects in macrocyclic systems formed by metalloporphyrins for their potential application in solar cells
(Universidad Andrés Bello, 2012) Zárate Bonilla, Ximena del Pilar.; Arratia Pérez, Ramiro; Facultad de Ciencias Exactas.
Dye-sensitized solar cells (DSCs) were designed by Michael Griitzel. They have become as a promising inexpensive alternative to light-current conversion. Basically, DSCs are constituted by nanocrystalline films of a semiconductor oxide, a !ayer of dye adsorbed to the oxide surface, solution of iodide/triiodide redox couple that by its reduction regenerates the dye after the electron-injection to the semiconductor. Nowadays, continuous researches are being carried out because of the variety of elementary components present in these cells. The process of current generation starts with the photo-excitation of the dye molecules, being this, the most important topic that has attracted a considerable experimental and theoretical interest. Studies point to different kind of dyes that allow tuning the properties and then to optimize their overall performance in assembled devices. The dyes show interesting properties useful in the design of a DSC, namely light absorption in the UV-Visible region of the electromagnetic spectrum, chemical stability, sensitization, effective adsorption on the semiconductor surface, electron-separated states, etc. Among the wide amount of dyes employed, porphyrinic systems have shown to be efficient lightharvesting. In this sense, properties of different families constituted by monomers, dimers and trimers of porphyrinic macrocycles coordinated to metals like Ti, Ni and Zn were studied. The structural modification consists in changing the peripheral 13-substituents in the rings with the proposal to predict the geometrical and electronic properties of new complexes which can be good candidates as sensitizers in solar cells. In addition, the study of electron-injection mechanisms from dyes to a TiO2 nanoparticle was performed since a theoretical point of view. In general, the results show that complexes with electron donor peripheral substituents are very promising to provide good performances as sensitizers and they could act as light-harvesting for DSCs. On the other hand, it was found a theoretical tool which allows differentiation of the direct and indirect photo electron-injection mechanisms in a DSC.
Phenomenological chemical reactivity theory for mobile electrons
(Universidad Andrés Bello, 2009) González Suárez, José Mauricio.; Renato Contreras.; Facultad de Ciencias Exactas.
We present herein a model to
Relativistic study of the luminescent properties in systems containing lanthanide and actinide ions : a view of the antenna effect
(Universidad Andrés Bello, 2017) Cantero López, Plinio de los Santos Plinio de los Santos.; Arratia Pérez, Ramiro; Facultad de Ciencias Exactas.
In the recent decades, the synthesis and the theoretical study of new compounds containing Lanthanide and Actinide ions have become in a very interesting topic of research. Ali this due to the potential use ofthis systems as materials for biological immunoassays, lasers, cathode ray tubes, lighting systems, electroluminescent devices, sensors, dosimeters, imaging agents, display applications, decoration purposes and light-emitting diodes (LEDs). These unique spectroscopic properties are attributed to the characteristic f-f transitions in their inner ( 4f/5f) shell, which is shielded from the influence of the environment by the outer (5s,5p/6d,7s) shells. These transitions are Laporte-forbidden with low absorption coefficient, which makes the direct excitation of the Ln/ An ion inefficient. For this purpose, over the years have been preved that the complexation by certain organic and organometallic ligands favored and enhances the luminescence intensity ofthese ions (Antenna effect), due to the ligand absorb highly efficiently the light in the ultraviolet region and transfers energy from its excited level to the resonant level of the Ln/An center (charge/energy transfer process), which can ernit light or decay nonradiatively. In this context, this doctoral thesis entitled: "Relativistic Study of the Luminescent Properties in Systems Containing Lanthanide Ions and Actinide" we study the Antenna effect and the electronic structure of the Ln/An systems using quantum chemical relativistic methods (relativistic density functional). In a first step, we investigated heterobimetallic systems of Actinide and transition metals unsupported by bridging ligands. Our aim was to research the role of the [CpM(C0)2r (M= Fe, Ru, Os) chromophore in the optical properties of the [Cp2ThMCp(C0)2]+ complexes. In the next stage, was shown the possibility of tuning the molecular antenna effect in these molecules by means of structural modifications in the peripheral ligands. Finally, were synthesized new luminescent Eu(III) complexes, based on dypiridophenazine (dppz) derivatives ligands. Apart from the Relativistic DFT, these compounds were also theoretically studied by means of ab initio methods that allows excited states in Lanthanide complexes to be analyzed, and energy transfer pathways from the antenna to Lanthanide ion.
Electrochemical behaviors and relativistic DFT calculations to understand the terminal ligand influence on the [Re₆(μ₃-Q)₈X₆]⁴- clusters : synthesis and photochemistry
(Universidad Andrés Bello, 2018) Rojas Poblete, Macarena Gemita; Ramiro Arratia Pérez.; Facultad de Ciencias Exactas
ehalcogenide compounds of hexarhenium (111), have been extensively studied in recent years, these compounds possess a series of physical and chemical properties, which have been investigated in solid state and in solution. In this line, the new hexarhenium cluster of coordination with 2,6-(dipirid-3-il)-4- cyanophenilpyridine, was synthesized, and a series of tests were carried out to analyze its potentinl use as an antitumoral agent and biomarker, especially due to the interesting fluorescence that presents in the near infra red region (NIR). A Born-Haber thermodynamic cycle was used to determine the redox potential in a series of hexarhenium (111) clusters of the form [Re6(μr0)8X6]4. where Q =s2• and Se 2 • and X = F·, er, Br", r, eN·, Ne·, SeN·, Nes·, OeN· and Neo·. Frequency analysis, relativistic and solvent effects were considered to estimate the free energy of the reversible process Relll6/Re1115 RelV at the DFT level. AII the redox potentials were reported with regards to the standard hydrogen electrode (SHE) and are in reasonable agreement with the available experimental results. In general, the molecular orbitals involved in the redox process were localized in the cluster core [Re6(μ3-Q)8]2\ and therefore the peripheral ligands act only as a modifier of the crystal-field strength, influencing the energy of the frontier molecular orbital splitting. Additionally, the theoretical approach was validated using an experimental protocol to study the electrochemical behavior of the [Re6(μrSe)816]3 " cluster. An important first reversible reduction process was found at E112 = +0.47 V (SHE), which is in good agreement with the value predicted theoretically in this investigation.
Selectivity and binding : a survey into the host-guest formation towards the designing of supramolecular arrays
(Universidad Andrés Bello, 2015) Olea Ulloa, Carolina Paz; Ramiro Arratia Pérez.; Facultad de Ciencias Exactas
El término "Host-guest chemistry" se utiliza para designar sistemas supramoleculares, en donde una molécula pequeña ("guest") es capaz de alojarse dentro de la cavidad de otra ("host"). Este tipo de sistemas son llamados complejos de inclusión, o bien, complejo "Host-guest". Las interacciones que dan cuenta del ingreso del "guest" en la cavidad del "host" son fuerzas de carácter débil, las cuales incluyen interacciones tipo puentes de hidrógeno, ión - dipolo, fuerzas de dispersión, etc. Distintas moléculas hospederas ("host) han sido desarrolladas y caracterizadas con el fin de estudiar este tipo de complejos. Dentro de los que destacan Calixarenos, Ciclodextrinas, Éter de Corona, Cucurbituril, Ciclofanos, entre otras. Los que, dependiendo del tamaño de sus cavidades y de los grupos funcionales que los conforman, son capaces de interaccionar con distintas estructuras "guest" mediante interacciones no covalentes. En el marco de La Teoría de la Funcional de la Densidad (DFT) se optimizarán las geometrías de distintos macrociclos hospederos, además de una variedad de moléculas que puedan alojarse en ellos, como también diversos complejos de inclusión que puedan formarse entre ambas estructuras. Esto, con el fin de estudiar y caracterizar las distintas interacciones que ocurren en la formación de dicho complejo supramolecular, para así poder comprender la selectividad entre dos moléculas involucradas en los complejos de inclusión.
Theoretical study on the catalytic bond activation mediated by lanthanide and actinide ions in gas phase
(Universidad Andrés Bello, 2014) Murillo López, Juliana Andrea; Arratia Pérez, Ramiro.; Facultad de Ciencias Exactas
The activation of chemical bonds has a great interest in modern chemistry because it makes possible the use of commonly non-reactive molecules, but abundant, as synthetic precursors, among others. Sorne decades ago it was found that metallic ions could activate C-H and C-C bonds, for that so much effort was devoted in studying the activation of hydrocarbons mainly by transition metals. But, due to the unique properties of lanthanides and actinides elements, there is an increased interest in studying how these elements could catalyze, in a more efficient way, the activation of such bonds. So far there have been few theoretical works that have studied in depth the kinetic and thermodynamic of these reactions using sophisticated electronic structure methods including relativistic effects, which determine the chemistry of the lanthanides and actinides. In the present investigation we proposed, by using theoretical and computational relativistic quantum chemistry methodologies, the study and molecular modeling of chemical reactions between lanthanides and actinides ions with small molecules, as simple aliphatic systems, in order to study the catalytic activation of unreactive bonds. Is of special interest the determination of the rate constants and the activation parameters that govern each reaction, as well as the calculation of molecular properties that allow the characterization of the proposed mechanism of each reaction under study.
Microlensing events and old stellar populations around the galactic centre
(Universidad Andrés Bello, 2021) Navarro, María Gabriela; Capuzzo-Dolcetta, Roberto; Facultad de Ciencias Exactas
Among the most critical unknowns in astrophysics concern understanding the nature of galaxies. Galactic formation, structure, and evolution have been studied for several years, using observations, which are improving in quality with the new generation of telescopes, and computational methods that implement sophisticated models to reproduce what we observe. However, we have not yet been able to fully understand the characteristics of spiral galaxies, such as the Milky Way. In this context, we consider two independent indicators. Microlensing events: caused by a partial alignment between point-like objects. Their purely geometrical nature reveals the structure and dynamics of stellar systems. And RR Lyrae stars; distance indicators and tracers of old and metal-poor stellar populations. They are versatile objects to study the formation and 3D structure of stellar systems. Using the near-IR observations with the VISTA Variables in the Vía Láctea Survey (VVV), we examine the populations located in the reddened areas surrounding the Galactic center and at low latitudes of the Galactic bulge. We compare the observations with theoretical studies of Galactic formation to understand the functioning of the Milky Way, from its origin to how we currently observe it.
Propiedades magnéticas en compuestos de coordinación con potenciales aplicaciones en espintrónica y electrónica molecular : un estudio teórico
(Universidad Andrés Bello, 2017) Montenegro Pohlhammer, Nicolás Eduardo.; Facultad Ciencias Exactas
En los últimos años, los imanes moleculares o "Single Molecule Magnets" (SMM) han atraído la atención de muchos investigadores ya que sus propiedades los convierten en candidatos idóneos para ser los bloques de construcción de futuras unidades de almacenamiento de datos, portadores de bits cuánticos o componentes de dispositivos espintrónicos. En la siguiente investigación se presenta un estudio teórico de las propiedades magnéticas de diferentes compuestos de coordinación con metales de transición de la primera serie con especial énfasis en el complejo Mn(IIIh (µ-F)F4(Me3tacn)2 . La interpretación de la respuesta magnética en complejos metálicos es por lo general compleja debido a que es el resultado de la combinación de varios fenómenos. En primer lugar los estados electrónicos de los iones metálicos están determinados por el campo de ligandos y el acoplamiento espín-orbital y en muchos casos la descripción teórica de estos compuestos requiere el uso de métodos multideterminantales debido a la alta correlación electrónica. La determinación de los parámetros del Hamiltoniano de espín es un reto tanto para los trabajos experimentales como para los teóricos y en particular la aplicación de las herramientas de la Química Computacional y Teórica es crucial ya que permite en primer lugar validar los Hamiltonianos de espín (fenomenológicos), discutir e interpretar los parámetros experimentales y correlacionar la estructura de los compuestos con su respuesta magnética, lo que garantiza una mejor comprensión de la relación entre geometría, estructura electrónica y propiedades magnéticas. El objetivo del presente trabajo es diseñar y caracterizar teóricamente complejos metálicos con potencial uso como SMM y en espintrónica. Soportados por la hipótesis de que las herramientas de la Química Computacional y Teórica y específicamente los métodos multideterminantales (CASSCF, MRCI, DDCln etc.) permiten una descripción profunda de la magnetoquímica de los compuestos de coordinación con metales de la primera serie.
Study of cyclic metal-ligand complexes containing closed-shell coinage metals : formation and consequence of bonding interactions between the d10-d10 centers
(Universidad Andrés Bello, 2015) Guajardo Maturana, Raúl.; Muñoz Castro, Álvaro; Facultad de Ciencias Exactas
Supramolecular chemistry has attracted the attention of several research groups due to it constitutes a significant step toward the design and development of molecular devices and new materials. In materials science, functional complexes containing monovalent Au(I), Ag(I), Cu(I) metal ions with d1º closed-shell interactions exhibit an interesting set of properties related to supramolecular aggregation, such as photoluminescence, catalysis, molecular magnetism, making them suitable for to a wide variety of technological application. We focus on multimetallic system, where several closed-shell metal centers are stabilized with organic ligand, leading to a two dimensional core of three or more metallic atoms linked to sigma-donor ligands involving both metal-metal and metalligand interactions, retaining the metallic core.
Theoretical study of molecular donor/acceptor semiconductors for tandem photovoltaic cells
(Universidad Andrés Bello, 2013) Aparecida Barboza, , Cristina.; MacLeod-Carey, Desmond; Arratia Pérez, Ramiro
In this Thesis quantum chemical tools have been used to gain more information about physicochemical properties of organic and inorganic molecules that could be used as semiconductors for photovoltaic ce lis of tandem type. Into this context, severa( levels of theory have been used to validate the methodologies chosen for the calculations, fron density functional have been used to validate the methodologies chosen for the calculations, f om density functional theory (DFT and time dependent-DFT) to post-Hartree-Fock methods (Coupled-Cluster Singles and Doubles - CCSD). Fluorene, a model molecule used as semiconductor for organic electronics was employed to carry out this benchmark study. Following an analysis of the structural and optical prope1ties of dimers of fluorenes, pentalenes and indenofluorenes (fluorenacenes and fluorenaphenes) derivatives were done. The electronic delocalization of these molecules were also evaluated, due to their importance in the processes of charge transfer that occur in photovoltaic devices. Besides on the organic molecules, properties of copper clusters were also calculated, in order to evaluate if those molecules could also be used as semiconductors. Our results suggest that is possible to modulate the electronic properties of the compounds studied, as well to combine them in order to get a better coverage of the solar spectrum, leading to a more efficient photovoltaic solar device. The strong directionality of the electronic transitions of the copper clusters indicates that them could be used as donor materia Is, while the organic small molecules could be used as acceptors, improving the charge transfer in photovoltaic solar devices.

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