Estudo da geometria da uréia por métodos ab initio e simulação computacional de líquidos

A study was carried out on the urea geometries using ab initio calculation and Monte Carlo computational simulation of liquids. The ab initio calculated results showed that urea has a non-planar conformation in the gas phase in which the hydrogen atoms are out of the plane formed by the heavy atoms. Free energies associated to the rotation of the amino groups of urea in water were obtained using the Monte Carlo method in which the thermodynamic perturbation theory is implemented. The magnitude of the free energy obtained from this simulation did not permit us to conclude that urea is non-planar in water.

Hintariskienhallinta pitkäaikaisissa urakoissa

Pitkäaikaisten rakennusurakoiden tarjouslaskennassa on ennakoitava hintojen muutoksia useiden vuosien päähän, kun tarjoukset on tehtävä kiinteillä hinnoilla. Kustannusten ennakointi ja hintariskienhallinta on kriittinen tekijä rakennusalan yrityksen kilpailukyvylle. Tämän tutkielman tavoitteena on kehittää YIT Rakennus Oy:n Infrapalveluille toimintamalli ja työkalu, joiden avulla hintariskejä voidaan hallita tarjouslaskennassa sekä hankintatoimessa. Ratkaisuksi kehitettiin kustannusten ennakointi -malli, jossa panosryhmien hintojen kehitystä ennustetaan asiantuntijaryhmissä säännöllisesti. Kustannusten ennakointi -mallin käyttöönotto vaatii ennustettavien panosryhmien määrittelyä. Lisäksi on nimettävä asiantuntijaryhmä sekä valittava aikajänne, jolle ennuste tehdään. Ennusteisiin sisältyvä epävarmuus saadaan esiin Monte Carlo simulaatiolla, ja urakan hintariskiä voidaan siten arvioida todennäköisyysjakaumien ja herkkyysanalyysin avulla. Valmiita ennusteita hyödynnetään tarjouslaskennassa sekä hankintatoimessa taktiikoiden ja strategioiden valinnassa.

Hankintaprosessin suorituskyvyn arviointi ja kehittäminen

Tämän työn tarkoituksena oli tarkastella kohdeorganisaation hankintaprosessin suorituskykyä. Tutkimuksen päämääränä oli tuottaa yritykselle sellaista tietoa ja arviointikriteerejä, joiden avulla yritys voi kehittää valmiuksiaan oman suorituskyvyn tehokkaampaan arviointiin tulevaisuudessa. Tutkielma tehtiin Skanska Oy:n osto-osastolle Helsinkiin. Tutkimuksen kohteeksi valittiin kausisopimusten hankintaprosessi epäsuorissa hankinnoissa, kotimaisilla markkinoilla. Keskitetyn kausisopimusten hankintaprosessin tarkoituksena on tuottaa yritykselle kilpailukykyisiä sopimuksia sekä saavuttaa prosessin parempi hallinta ja läpinäkyvyys. Tietoa tutkimuksen kohteena olevasta prosessista kerättiin haastatteluilla ja keskustelutuokioilla sekä yrityksen dokumenteista. Aineiston keräämisen kautta pyrittiin saamaan syvempi kuva prosessin toiminnasta, sen ongelmakohdista sekä niiden syistä ja seurauksista. Toisen tarkastelunäkökulman prosessin arvioinnille tarjosi läpimenoajan mittaaminen. Saatua aineistoa luokiteltiin vika- ja vaikutusanalyysiin pohjautuvalla mallilla sekä Monte Carlo – simulaatiomenetelmään perustuvalla ohjelmalla. Työn tuloksena esitetään tutkimuksen kohteena olevalle prosessille sopivia kehitystoimenpiteitä sekä suositeltavia prosessin mittaamisalueita.

Multicointegration, polynomial cointegration and I(2) cointegration with structural breaks. An application to the sustainability of the US external deficit

In this paper we model the multicointegration relation, allowing for one structural break. Since multicointegration is a particular case of polynomial or I(2) cointegration, our proposal can also be applied in these cases. The paper proposes the use of a residualbased Dickey-Fuller class of statistic that accounts for one known or unknown structural break. Finite sample performance of the proposed statistic is investigated by using Monte Carlo simulations, which reveals that the statistic shows good properties in terms of empirical size and power. We complete the study with an empirical application of the sustainability of the US external deficit. Contrary to existing evidence, the consideration of one structural break leads to conclude in favour of the sustainability of the US external deficit.

O método das trajectórias clássicas: colisões coplanares do tipo A+BC

The general methodology of classical trajectories as applied to elementary chemical reactions of the A+BC type is presented. The goal is to elucidate students about the main theoretical features and potentialities in applying this versatile method to calculate the dynamical properties of reactive systems. Only the methodology for two-dimensional (2D) case is described, from which the general theory for 3D follows straightforwardly. The adopted point of view is, as much as possible, that of allowing a direct translation of the concepts into a working program. An application to the reaction O(¹D)+H2->O+OH with relevance in atmospheric chemistry is also presented. The FORTRAN codes used are available through the web page www.qqesc.qui.uc.pt.

Local noise analysis of a Schottky contact: combined thermionic-emissiondiffusion theory

A theoretical model for the noise properties of Schottky barrier diodes in the framework of the thermionic-emission¿diffusion theory is presented. The theory incorporates both the noise inducedby the diffusion of carriers through the semiconductor and the noise induced by the thermionicemission of carriers across the metal¿semiconductor interface. Closed analytical formulas arederived for the junction resistance, series resistance, and contributions to the net noise localized indifferent space regions of the diode, all valid in the whole range of applied biases. An additionalcontribution to the voltage-noise spectral density is identified, whose origin may be traced back tothe cross correlation between the voltage-noise sources associated with the junction resistance andthose for the series resistance. It is argued that an inclusion of the cross-correlation term as a newelement in the existing equivalent circuit models of Schottky diodes could explain the discrepanciesbetween these models and experimental measurements or Monte Carlo simulations.

Effect of long-range Coulomb interaction on shot-noise suppression in ballistic transport

We present a microscopic analysis of shot-noise suppression due to long-range Coulomb interaction in semiconductor devices under ballistic transport conditions. An ensemble Monte Carlo simulator self-consistently coupled with a Poisson solver is used for the calculations. A wide range of injection-rate densities leading to different degrees of suppression is investigated. A sharp tendency of noise suppression at increasing injection densities is found to scale with a dimensionless Debye length related to the importance of space-charge effects in the structure.

Universality of the 1/3 shot-noise suppression factor in nondegenerate diffusive conductors

Shot-noise suppression is investigated in nondegenerate diffusive conductors by means of an ensemble Monte Carlo simulator. The universal 1/3 suppression value is obtained when transport occurs under elastic collision regime provided the following conditions are satisfied: (i) The applied voltage is much larger than the thermal value; (ii) the length of the device is much greater than both the elastic mean free path and the Debye length. By fully suppressing carrier-number fluctuations, long-range Coulomb interaction is essential to obtain the 1/3 value in the low-frequency limit.

Local noise analysis of a Schottky contact: combined thermionic-emissiondiffusion theory

A theoretical model for the noise properties of Schottky barrier diodes in the framework of the thermionic-emission¿diffusion theory is presented. The theory incorporates both the noise inducedby the diffusion of carriers through the semiconductor and the noise induced by the thermionicemission of carriers across the metal¿semiconductor interface. Closed analytical formulas arederived for the junction resistance, series resistance, and contributions to the net noise localized indifferent space regions of the diode, all valid in the whole range of applied biases. An additionalcontribution to the voltage-noise spectral density is identified, whose origin may be traced back tothe cross correlation between the voltage-noise sources associated with the junction resistance andthose for the series resistance. It is argued that an inclusion of the cross-correlation term as a newelement in the existing equivalent circuit models of Schottky diodes could explain the discrepanciesbetween these models and experimental measurements or Monte Carlo simulations.

Impedance field and noise of submicrometer n+ nn+ diodes: analytical approach

A theoretical model for the noise properties of n+nn+ diodes in the drift-diffusion framework is presented. In contrast with previous approaches, our model incorporates both the drift and diffusive parts of the current under inhomogeneous and hot-carrier conditions. Closed analytical expressions describing the transport and noise characteristics of submicrometer n+nn+ diodes, in which the diode base (n part) and the contacts (n+ parts) are coupled in a self-consistent way, are obtained

Estrutura e propriedades de elipticinas

The ellipticines constitute a broad class of molecules with antitumor activity. In the present work we analyzed the structure and properties of a series of ellipticine derivatives in the gas phase and in solution using quantum mechanical and Monte Carlo methods. The results showed a good correlation between the solvation energies in water obtained with the continuum model and the Monte Carlo simulation. Molecular descriptors were considered in the development of QSAR models using the DNA association constant (log Kapp) as biological data. The results showed that the DNA binding is dominated by electronic parameters, with small contributions from the molecular volume and area.

Análise de imagem em química analítica: empregando metodologias simples e didáticas para entender e prevenir o escurecimento de tecidos vegetais

A simple and didactic experiment was developed for image monitoring of the browning of fruit tissues caused by the enzyme polyphenol oxidase. The procedure, easy and inexpensive, is a valuable tool to teach and demonstrate the redox reaction between the enzyme and the natural polyphenols. To obtain the browning percentage for apple, pear and banana, digital photographs were employed, and the images were analyzed by means of Monte Carlo methods and digital analysis programs. The effects of several experimental conditions were studied, such as pH, light, temperature and the presence of oxygen or anti-oxidants. It was observed that each fruit presented a different condition that better minimized the oxidation process. The absence of oxygen and the application of a bissulphite solution were sufficient to keep the quality of all fruits tested.

Probing quantum gravity using photons from a flare of the active galactic nucleus Markarian 501 observed by the MAGIC telescope

We analyze the timing of photons observed by the MAGIC telescope during a flare of the active galactic nucleus Mkn 501 for a possible correlation with energy, as suggested by some models of quantum gravity (QG), which predict a vacuum refractive index similar or equal to 1 + (E/M-QGn)(n), n = 1, 2. Parametrizing the delay between gamma-rays of different energies as Delta t = +/-tau E-1 or Delta t = +/-tau E-q(2), we find tau(1) = (0.030 +/- 0.012) s/GeV at the 2.5-sigma level, and tau(q) = (3.71 +/- 2.57) x 10(-6) s/GeV2, respectively. We use these results to establish lower limits M-QG1 > 0.21 X 10(18) GeV and M-QG2 > 0.26 x 10(11) GeV at the 95% C.L. Monte Carlo studies confirm the MAGIC sensitivity to propagation effects at these levels. Thermal plasma effects in the source are negligible, but we cannot exclude the importance of some other source effect.

Random walk radiosity with generalized absorption probabilities

The author studies random walk estimators for radiosity with generalized absorption probabilities. That is, a path will either die or survive on a patch according to an arbitrary probability. The estimators studied so far, the infinite path length estimator and finite path length one, can be considered as particular cases. Practical applications of the random walks with generalized probabilities are given. A necessary and sufficient condition for the existence of the variance is given, together with heuristics to be used in practical cases. The optimal probabilities are also found for the case when one is interested in the whole scene, and are equal to the reflectivities

Critical behavior in nonequilibrium phase transitions

The nonequilibrium phase transitions occurring in a fast-ionic-conductor model and in a reaction-diffusion Ising model are studied by Monte Carlo finite-size scaling to reveal nonclassical critical behavior; our results are compared with those in related models.