Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Adsoption-induced restructuring of gold nanochains

The chemical properties of single-atomic chains of gold atoms are investigated using density functional calculations. The nanochains are shown to be unusually chemically active with strong chemisorption of oxygen atoms and carbon monoxide. The chemisorption energies vary significantly with the strain/stress conditions for the chain. Oxygen atoms are found to energetically prefer to get incorporated into a chain forming a new type of gold-oxygen nanochain with a conductance of one quantum unit. We suggest that the long bond lengths observed in electron microscopy investigations of gold chains can be due to oxygen incorporation.

Theoretical modeling of photon and electron-stimulated Na and K desorption from SiO2

The mechanism of generation of atomic Na and K from SiO2 samples has been studied using explicitly correlated wave function and density functional theory cluster calculations. Possible pathways for the photon and electron stimulated desorption of Na and K atoms from silicates are proposed, thus providing new insight on the generation of the tenuous Na and K atmosphere of the Moon.

MgO/Ag(001) interface structure and STM images from first principles

The interface of MgO/Ag(001) has been studied with density functional theory applied to slabs. We have found that regular MgO films show a small adhesion to the silver substrate, the binding can be increased in off-stoichiometric regimes, either by the presence of O vacancies at the oxide film or by a small excess of O atoms at the interface between the ceramic to the metal. By means of theoretical methods, the scanning tunneling microscopy signatures of these films is also analyzed in some detail. For defect free deposits containing 1 or 2 ML and at low voltages, tunnelling takes place from the surface Ag substrate, and at large positive voltages Mg atoms are imaged. If defects, oxygen vacancies, are present on the surface of the oxide they introduce much easier channels for tunnelling resulting in big protrusions and controlling the shape of the image, the extra O stored at the interface can also be detected for very thin films.

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.

Timing and nature of alluvial fan and strath terrace formation in the Eastern Precordillera of Argentina

Sixty-eight 10Be terrestrial cosmogenic nuclide (TCN) surface exposure ages are presented to define the timing of alluvial fan and strath terrace formation in the hyper-arid San Juan region of the Argentine Precordillera. This region is tectonically active, and numerous fault scarps traverse Quaternary landforms. The three study sites, Marquesado strath complex, Loma Negra alluvial fan and Carpintería strath complex reveal a history of alluvial fan and strath terrace development over the past w225 ka. The Marquesado complex Q3m surface dates to w17 3 ka, whereas the Loma Negra Q1ln, Q2ln, Q3ln, Q4ln, and Q5ln surfaces date to w24 3 ka, w48 2 ka, w65 13 ka, w105 21 ka, and w181 29 ka, respectively. The Carpintería complex comprises eight surfaces that have been dated and include the Q1c (w23 3 ka), Q2c (w5 5 ka), Q3ac (w25 12 ka), Q3bc (w29 15 ka), Q4c (w61 12 ka), Q5c (w98 18 ka), Q6c (w93 18 ka), and Q7c (w212 37 ka). 10Be TCN depth profile data for the Loma Negra alluvial fan complex and Carpintería strath terrace complex, as well as OSL ages on some Carpintería deposits, aid in refining surface ages for comparison with local and global climate proxies, and additionally offer insights into inheritance and erosion rate values for TCNs (w10 104 10Be atoms/g of SiO2 and w5 m Ma 1, respectively). Comparison with other alluvial fan studies in the region show that less dynamic and older preserved surfaces occur in the Carpintería and Loma Negra areas with only younger alluvial fan surfaces preserved both to the north and south. These data in combination with that of other studies illustrate broad regional agreement between alluvial fan and strath terrace ages, which suggests that climate is the dominant forcing agent in the timing of terrace formation in this region.

Molecular Physics of Elementary Processes relevant to Hypersonics: atom-molecule, molecule-molecule and atom-surface processes.

In the present chapter some prototype gas and gas-surface processes occurring within the hypersonic flow layer surrounding spacecrafts at planetary entry are discussed. The discussion is based on microscopic dynamical calculations of the detailed cross sections and rate coefficients performed using classical mechanics treatments for atoms, molecules and surfaces. Such treatment allows the evaluation of the efficiency of thermal processes (both at equilibrium and nonequilibrium distributions) based on state-to-state and state specific calculations properly averaged over the population of the initial states. The dependence of the efficiency of the considered processes on the initial partitioning of energy among the various degrees of freedom is discussed.

Algumas Considerações sobre a Regra de Hund e a Estrutura Eletrônica de Átomos no Ensino de Química

Hund's maximum multiplicity rule as stated in most elementary and intermediate level textbooks on general and inorganic chemistry and usually taught at the college and undergraduate level is incorrect. It is true that electrons entering a subshell of an atom tend to occupy the orbitals singly as far as possible but not necessarily with parallel spins. Also, proper definitions and correct use of terms like configuration, microstate, spectroscopic term, level and state are essential if confusion on the part of the student, especially the beginner, is to be avoided.

A Eterna Busca do Indivisível: do Átomo Filosófico aos Quarks e Léptons

The fascinating search of the inner boundaries of the Universe, has been entangled, since the birth of greek philosophy 25 centuries ago, with the main epistemological changes in the History of Science. This paper does not intend to present a systematic description of the discovery of the elementary particles. By stressing the main achievements of the knowledge of matter's structure and their dependence on symmetry arguments, it is argued that even considering profound differences in each historical period, there is a paradgima of atom shared by Chemistry and Particle Physics. This text could help High School Teachers of Chemistry and Physics, as well as motivate them, in the challenge of explaining to their pupils how the idea of atom evolved.

Walter Charleton (1620 - 1707) e sua Teoria Atômica

Several authors in the 17th century used the atomic hypothesis to explain observable phenomena. This paper analyzes some ideas about chemical transformation proposed by the English physician Walter Charleton. In Physiologia Epicuro-Gassendo-Charltoniana (London, 1654), Charleton examined philosophical aspects of the atomic theory, and suggested that the best explanation for all natural phenomena would be only in terms of atoms and their motions. Sometimes, however, he had to attribute to the atoms some kind of "internal virtue", to explain more complex properties of the matter. His idea of "element", and the little use of experimentation and quantification, also limited the range of Charleton's theory.

O relevante papel do agente sililante na modificação de superfícies de polímeros

The applicability of the silylant agents of the general formula Y3Si-R-X, depends on the reactivity of Y group (halide or alcoxide) attached to silicon and the organic function X (halide, amine, thiol, cyanide, etc) in the extreme position of the chain. Both groups are linked together by an organic chain R, containing usually three methylene groups. A series of these agents can be covalently bonded to an inorganic matrix, since the available OH groups are distributed on the surface, making silica gel the most common support. However, other inorganic oxides, zeolites, lamellar inorganic phosphates and chrysotile can also have these agents anchored. Some illustration are presented for immobilized surface in the use as extractors of cations from dilute aqueous or non-aqueous solutions, catalysts agents, ionic exchanged materials, support for enzyme immobilization, chromatographic applications, use in some industrial features and in many other areas. The evolution of this exciting research field to produce new materials, for many tecnological applications, is strongly dependent on the development of a sensible systematic process for the synthesis of a series of new specific silylant agents.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.

Sinkkirikasteen liukenemisnopeuteen vaikuttavat tekijät ja sinkkirikasteen suoraliuotuksen mallintaminen

Työn kirjallisuusosassa selvitettiin eri tekijöiden (lämpötila, paine, mineralogia, partikkelikoko, sekoitus, kiintoainepitoisuus, liuoksen happo-, rauta- ja happipitoisuus) vaikutusta sinkkirikasteen suoraliuotusprosessin tärkeimpiin ilmiöihin (diffuusio, aineensiirto, reaktiokinetiikka). Kirjallisuusosassa kartoitettiin myös tämän hetkistä tietämystä niistä tekijöistä, jotka ovat oleellisia, kun sinkkirikasteen suoraliuotusprosessia mallinnetaan. Näitä tekijöitä ovat: sinkkirikasteiden liuotuksen kemia, sinkkirikasteiden liuotuksen kinetiikka ja mekanismit, kaasuneste aineensiirto ja kiinteäneste aineensiirto. Lisäksi selvitettiin millä tavoin aikaisemmissa tutkimuksissa sinkkirikasteiden suoraliuotusta on mallinnettu. Mallinnusosassa käsiteltiin atmosfääristä sinkkirikasteen suoraliuotusta, jossa hapettimena toimi ferri(III)rauta. Mallintamisessa käytettiin kirjallisuudessa esitettyjä mittaustuloksia ja mallintaminen tehtiin Modest tietokoneohjelmistolla. Työssä tehty atmosfäärisen suoraliuotuksen mallintaminen labo-ratoriomittakaavassa (laimeat liuokset ja pienet kiintoainepitoisuudet) antoi lupaavia tuloksia. Ongelmia mallin ennustuksen kanssa esiintyi pienissä happopitoisuuksissa, alhaisissa lämpötiloissa sekä pienillä ja suurilla partikkeleilla. Työn kirjallisuusosassa tunnistettiin ne ongelmakohdat, jotka vaativat lisätutkimuksia, jotta sinkkirikasteen atmosfääriselle suoraliuotukselle pystytään kehittämään simulointimalli. Näitä ovat: 1. Hapen liukoisuus ja aineensiirto teollisuuden käyttämissä sinkkirikastelietteissä, 2. Sopivien mittaustulosten puuttuminen, jotta atmosfääristä suoraliuotusta, jossa O2 ja Fe3+ toimivat hapettimena voitaisiin mallintaa, 3. Kiinteäneste aineensiirron merkitys sinkkirikasteen suoraliuotuksessa. Mallinnusosassa osoitettiin, että mekanistisella mallintamisella voidaan simuloida sinkkirikasteen atmosfääristä suoraliuotusta ainakin laboratoriomittakaavassa. Työn perusteella voidaan todeta, että sinkkirikasteen atmosfääriselle suoraliuotukselle voidaan työssä ehdotettujen jatkotutkimusten avulla kehittää numeerinen mekanistinen malli, jolla atmosfääristä sinkkirikasteiden suoraliuotusprosessia voidaan simuloida eri olosuhteissa.

Sobre os nomes dos elementos químicos, inclusive dos transférmios

The names of the chemical elements in Brazilian portuguese are presented, including a discussion of corresponding Brazilian nomenclature rules and translation of some parts of the pertinent IUPAC rules. The rules for naming groups of elements in the periodic table, as well as those for the symbolic indication of atomic number, mass number and electric charge of atoms, are also presented.

Construção de modelos para ilustração de estruturas moleculares em aulas de química

This paper describes the construction of a kit of molecular model for illustration of molecular structure in chemical class using cheap materials. The atoms were represented by plastic spheres and the bonds between the atoms were made from plastic straws which were cut in the required length using a scale of 1.6 cm corresponding to 100 pm. Examples of adaptations made in this kit for didactical application are given.