Extraordinary mechanical properties of monatomic C3N2 chain

One-dimensional monatomic chains are promising candidates for technical applications in the field of nanoelectronics due to their unique mechanical, electrical and optical properties. In particular, we investigate the mechanical properties including Young's modulus, ultimate strength and ultimate strain, which are necessities for the stability of the materials by the Car-Parrinello molecular dynamics in this work. The comparative studies for the alternating carbon-nitrogen (C₃N₂) chain and carbon chains (carbyne) of different lengths show that the carbon-nitrogen (C-N) chain is obviously stronger and stiffer than carbynes. Thus the C-N chain, which has been found in decomposition products of the nitromethane explosive simulations, could be a superior nano-mechanical material than the carbyne chain. Furthermore, it is found that the bond order of weakest bond in monatomic chains is positively correlated with Young's modulus and ultimate strength of materials.

Insight into CO Activation over Cu(100) under Electrochemical Conditions

The reduction of CO₂ on copper electrodes has attracted great attentions in the last decades, since it provides a sustainable approach for energy restore. During the CO₂ reduction process, the electron transfer to CO_ads is experimentally suggested to be the crucial step. In this work, we examine two possible pathways in CO activation, i.e. to generate COH_ads and CHO_ads, respectively, by performing the state-of-the-art constrained ab initio molecular dynamics simulations on the charged Cu(100) electrode under aqueous conditions, which is close to the realistic electrochemical condition. The free energy profile in the formation of COH_ads via the coupled proton and electron transfer is plotted. Furthermore, by Bader charge analyses, a linear relationship between C-O bond distance and the negative charge in CO fragment is unveiled. The formation of CHO_ads is identified to be a surface catalytic reaction, which requires the adsorption of H atom on the surface first. By comparing these two pathways, we demonstrate that kinetically the formation of COH_ads is more favored than that of CHO_ads, while CHO_ads is thermodynamically more stable. This work reveals that CO activation via COH_ads intermediate is an important pathway in electrocatalysis, which could provide some insights into CO₂ electroreduction over Cu electrodes.

O piloto aviador militar : traços disposicionais, características adaptativas e história de vida

Tese de doutoramento, Psicologia (Psicologia da Social), Universidade de Lisboa, Faculdade de Psicologia, 2015

O futurismo russo: Maiakovsky ou a "Nuvem de calças"

Este breve ensaio sobre o poeta e escritor russo Vladimir Mayakovsky é uma modesta tentativa de contribuir para um (re)descobrimento ou para uma simples revisitação da produção literária russa do período soviético, que, por razões muitas vezes apenas de ordem política e não estética, caiu no esquecimento, não sendo traduzida na sua totalidade, como é o caso de Mayakovsky, ou, pura e simplesmente, sendo votada ao “ostracismo”, porque rotulada, a priori ou ab initio, como obras escritas dentro das paredes estreitas do “realismo socialista”, padecendo de falta de criatividade e norteandose, aberta ou dissimuladamente, pelos princípios rígidos e imutáveis de um totalitarismo inflexível. Contudo, nem toda a literatura soviética pode ser enquadrada no realismo socialista, valendo a pena conhecê-la e analisá-la.

Traités divers de saint Thomas et de Gilles de Rome.

Contient : I Fol. 1-28. " Expositio Boetii de Trinitate secundum fratrem T[homam]. Ab initio nativitatis mee investigabo et ponam in lucem scienciam illius. Sap. VII. Naturalis mentis humane intuitus pondere corruptibilis corporis... " ; II Fol. 29-44. Divers traités philosophiques, dont plusieurs sont probablement de saint Thomas, savoir : ; 1° Traité dont le commencement manque et dont les premiers mots conservés sont : " Quorum substantie vel nature differentes, horum et operationes differentes et quorum substantia est eadem... " ; 2° " [De generatione.] Eorum que generantur alia generantur in sublimi, alia in ymo. Ea que generantur in sublimi tria habent loca... " ; 3° " [De speculis.] Queritur de forma resultante in speculo que... lumen vel color videtur esse, queritur primo utrum sit vel non... " ; 4° " [De essentia.] Necesse est considerare primo quid essentia, quid substancia... " ; 5° ; 6° ; 7° ; III

Investigation of molecular polarizabilities and derivatives in halomethanes

The research undertaken was to obtain absolute Raman intensities for the symmetric stretching vibrations of the methyl halides, CH3X with (X=F, CI, Br), by experiment and theory. The intensities were experimentally measured using the Ar+ ion gas laser as excitation source, a Spex 14018 double monochromator and a RCA C-31034 photomultiplier tube as detector. These intensities arise from changes in the derivative of the polarizability (8 a'), with respect to vibration along a normal coordinate (8qi). It was intended that these derivatives obtained with respect to normal coordinates would be converted to derivatives with respect to internal coordinates, for a quantitative comparison with theory. Theoretical numerical polarizability derivatives for the stretching vibrations are obtained using the following procedure. A vibration was simulated in the molecule by increasi.ng and decreasing the respective bond by the amount ±o.oosA for the C-H bonds and ±o.oIA for the C-X (X=F, CI, Br) bond. The derivative was obtained by taking the difference in the polarizability for the equilibrium geometry and the geometry when a particular bond is changed. This difference, when divided by the amount of change in each bond and the number of bonds present results in the derivative of the polarizability with respect to internal coordinate i.e., !1u/!1r. These derivatives were obtained by two methods: I} ab initio molecular orbital calculation and 2} theory of atoms in molecules (AIM) analysis. Due to errors in the experimental setup only a qualitative analysis of the results was undertaken relative to the theory. Theoretically it is predicted that the symmetric carbonhalogen stretch vibrations are more intense than the respective carbon-hydrogen stretch, but only for the methyl chloride and bromide. The carbon fluorine stretch is less intense than the carbon-hydrogen stretch, a fact which is attributed to the small size and high electronegativity of the fluorine atom. The experimental observations are seen to agree qualitatively with the theory results. It is hoped that when the experiment is repeated, a quantitative comparison can be made. The analysis by the theory of atoms in molecules, along with providing polarizabilities and polarizability derivatives, gives additional information outlined below. The theory provides a pictorial description of the main factors contributing to the molecular polarizability and polarizability derivative. These contributions are from the charge transfer and atomic dipole terms i.e., transfer of charge from one atom to another and the reorganization of atomic electronic charge distribution due to presence of an electric field. The linear relationship between polarizability and molecular volume was also observed.

Elementary steps in aqueous proton transfer reactions : a first principles molecular dynamics study

La nature des acides dans un environnement aqueux est primordiale dans de nombreux aspects de la chimie et de la biologie. La caractéristique principale d'un acide est sa capacité à transférer un proton vers une molécule d'eau ou vers n'importe quelle base, mais ce procédé n'est pas aussi simple qu'il y paraît. Il peut au contraire être extrêmement complexe et dépendre de manière cruciale de la solvatation des différents intermédiaires de réaction impliqués. Cette thèse décrit les études computationnelles basées sur des simulations de dynamique moléculaire ab initio qui ont pour but d'obtenir une description à l'échelle moléculaire des divers procédés de transferts de proton entre acide et bases dans un milieu aqueux. Pour cela, nous avons étudié une serie de système, dont l'acide hydrofluorique aqueux, l'acide trifluoroacétique aqueux, et un système modèle constitué d'un phénol et d'une entité carboxylate reliés entre eux par une molécule d'eau en solution aqueuse. Deux états intermédiaires ont été identifiés pour le transfert d'un proton depuis un acide. Ces intermédiaires apparaissent stabilisés par un motif local de solvatation via des ponts H. Leurs signatures spectroscopiques ont été caractérisées au moyen de la spectroscopie infrarouge, en utilisant le formalisme de la dynamique moléculaire ab initio, qui inclut l'effet quantique nucléaire de manière explicite. Cette étude a aussi identifié trois chemins de réaction élémentaire, qui sont responsable pour le transfert d'un proton d'un acide à une base, ainsi que leurs échelles de temps caractéristiques. Les conclusions tirées de ces études sont discutées dans les détails, au niveau moléculaire, avec une emphase sur les comparaisons entre les résultats théoriques et les mesures expérimentales obtenues dans a littérature ou via des collaborateurs.

Absence of collective effects in Heisenberg systems with localized magnetic moments

Existence of collective effects in magnetic coupling in ionic solids is studied by mapping spin eigenstates of the Heisenberg and exact nonrelativistic Hamiltonians on cluster models representing KNiF3, K2NiF4, NiO, and La2CuO4. Ab initio techniques are used to estimate the Heisenberg constant J. For clusters with two magnetic centers, the values obtained are about the same for models having more magnetic centers. The absence of collective effects in J strongly suggests that magnetic interactions in this kind of ionic solids are genuinely local and entangle only the two magnetic centers involved.

Local character of magnetic coupling in ionic solids

Magnetic interactions in ionic solids are studied using parameter-free methods designed to provide accurate energy differences associated with quantum states defining the Heisenberg constant J. For a series of ionic solids including KNiF3, K2NiF4, KCuF3, K2CuF4, and high- Tc parent compound La2CuO4, the J experimental value is quantitatively reproduced. This result has fundamental implications because J values have been calculated from a finite cluster model whereas experiments refer to infinite solids. The present study permits us to firmly establish that in these wide-gap insulators, J is determined from strongly local electronic interactions involving two magnetic centers only thus providing an ab initio support to commonly used model Hamiltonians.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Analyse von Linienbreiten in Photoemissionsspektren zur Bestimmung von d-Lochlebensdauern in Kupfer und Silber

Hochaufgelöste Photoelektronspektroskopie ermöglicht die Untersuchung der Zerfallsdynamik angeregter Lochzustände im Festkörper. Durch Messung der intrinsischen Linienbreiten in den Spektren von Kupfer- und Silbereinkristallen werden die Lebensdauern von tiefliegenden d-Lochzuständen in diesen Edelmetallen bestimmt und mit Vielteilchenrechnungen verglichen. Insbesondere kann gezeigt werden (1) daß sich die d-Lochlebensdauern in Kupfer und Silber trotz unterschiedlicher Lage der d-Bänder ähnlich verhalten (2) daß keine quadratische Abhängigkeit gemäß des einfachen Modell eines freien Elektronengases beobachtet wird und (3) daß die Lochlebensdauern an der d-Bandoberkante von Kupfer und Silber stark zunehmen. Diese experimentellen Befunde legen eine weitgehende Entkopplung der Zerfallsdynamik von d-Löchern und sp-Elektronen nahe. Diese Deutung kann qualitativ durch ab-initio Rechnungen zur Lochlebensdauer bestätigt werden.

Total differential scattering cross section of {Ar^+}-Ar at 15 to 400 keV

We report on the measurement of the total differential scattering cross section of {Ar^+}-Ar at laboratory energies between 15 and 400 keV. Using an ab initio relativistic molecular program which calculates the interatomic potential energy curve with high accuracy, we are able to reproduce the detailed structure found in the experiment.

Influence of the interaction potential on simulated sputtering and reflection data

The TRIM.SP program which is based on the binary collision approximation was changed to handle not only repulsive interaction potentials, but also potentials with an attractive part. Sputtering yields, average depth and reflection coefficients calculated with four different potentials are compared. Three purely repulsive potentials (Meliere, Kr-C and ZBL) are used and an ab initio pair potential, which is especially calculated for silicon bombardment by silicon. The general trends in the calculated results are similar for all potentials applied, but differences between the repulsive potentials and the ab initio potential occur for the reflection coefficients and the sputtering yield at large angles of incidence.

Volume isotope shifts in low lying transitions of Au I

Electronic factors in the volume isotope shift have been calculated in an ab initio way with the relativistic Dirac-Fock method for a number of different optical single/and two-photon transitions in Au I. The agreement with a semi-empirical method is within 10% for the resonance transition. For this one and a few other transitions the effect of core excitation has been analyzed with the Multi-configuration Dirac-Fock method as well, and it was found to reduce the electronic factor in the order of 5 %.

Squeezed thermal phonons precurse nonthermal melting of silicon as a function of fluence

A femtosecond-laser pulse can induce ultrafast nonthermal melting of various materials along pathways that are inaccessible under thermodynamic conditions, but it is not known whether there is any structural modification at fluences just below the melting threshold. Here, we show for silicon that in this regime the room-temperature phonons become thermally squeezed, which is a process that has not been reported before in this material. We find that the origin of this effect is the sudden femtosecond-laser-induced softening of interatomic bonds, which can also be described in terms of a modification of the potential energy surface. We further find in ab initio molecular-dynamics simulations on laser-excited potential energy surfaces that the atoms move in the same directions during the first stages of nonthermal melting and thermal phonon squeezing. Our results demonstrate how femtosecond-laser-induced coherent fluctuations precurse complete atomic disordering as a function of fluence. The common underlying bond-softening mechanism indicates that this relation between thermal squeezing and nonthermal melting is not material specific.