Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Innovation Benchmark Study: Analysis of Innovation Processes in Finnish Companies

Liikevaihdon orgaaninen kasvu on ensisijainen tekijä ja haaste yritysjohdolle yrityksen omistaja-arvon kasvattamiseksi. Tutkimus tarkastelee suosivatko suomalaisyritykset pääasiallisesti olemassa olevaa liiketoimintaa palvelevia innovaatioita vai tukevatko nykyhetken toimintatavat myös uusia kasvua kiihdyttäviä radikaaleja innovaatioita. Lisäksi työ kartoitti suomalaisyritysten innovaatioprosessien kehitysalueita käyttäen itsearviointitutkimusta.Tulokset johtivat kolmeen johtopäätökseen. Tutkimus osoitti, että vastaajayritykset ovat keskittyneet innovaatiotoiminnassaan vahvasti ydinliiketoimintaansa, jättäen potentiaaliset kasvumahdollisuudet huomioimatta. Yritykset tavoittelevat maksimaalisia tuottoja keskittymällä tuotteidensa korkeaan suorituskykyyn. Lyhyen aikavälin epärealistiset tuotto-odotukset sekä projekteille suunnatut arviointikriteerit rajoittavat liiketoimintaa mullistavien radikaalien innovaatioiden kehittymistä organisaatiossa. Toiseksi, tutkimus osoitti, että suuri osa yrityksistä käyttää perinteisen projektien arviointi- ja kehitysprosessin lisäksi vaihtoehtoisia ja huonosti kontrolloitavissa olevia kehitysprosesseja, mikäli projektille annetaan kielteinen rahoituspäätös standardin prosessin sisällä. Kolmanneksi, suomalaisyritysten innovaatioprosesseissa paljastui merkittäviä puutteita mitattavien elementtien suhteen.

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Putting customers first : serving the American public : best practice in telephone service : Federal Consortium Benchmark Study Report /

Mode of access: Internet.

Unraveling a Benchmark for Sulphur Akin in the Cochin Estuarine System

The thesis deals with a benchmark study of dissolved and sedimentary sulphur compounds which play prominent roles in the prevailing redox conditions in the selected sites of Cochin estuarine system. Sulphur and its analogues play prominent roles in estuarine biochemical processes. A complete knowledge on the sulphur involvement in these processes is restricted due to the lacking of data on the organic sulphur compounds. Sulphate and sulphide in surface and bottom water and Sulphate, acid volatile sulphide and total sulphur in sediments were studied and correlated to know their interrelations in determining the redox condition of the environment. It also characterises the sediments of the sites on the basis of total organic carbon: total sulphur ratio. The study had attempted to decrease the concentration levels of sulphur in the sedimentary environment by the application of a remedial measure. Knowledge of sulphur uptake by plants from prior literatures has prompted to use phytoremediation for decreasing the sulphur concentration. Phytoremediation is an emerging technology that uses plants to clean up or remediate contaminated soil, sludges, sediments, and ground water through contaminant removal, degradation or containment. The plant selected was wheat grass since earlier studies have shown that wheat grass is effective in remediating pollutants particularly trace metals. So reduction in the concentration of selected trace metals was also focussed.

Estudo de Ferramentas FEA Comerciais na Simulação Numérica de Processos de Conformação de Chapas Metálicas. Aplicação à Indústria Automóvel.

Os componentes obtidos através da conformação plástica de chapas têm uma grande importância, tanto na etapa de concepção do produto como na etapa de produção na indústria automóvel. Isto comprova-se pelo facto de, em média, cada automóvel integrar cerca de 500 componentes estampados para construir o chassis e a carroçaria [Alves 2003]. Deste total de componentes, 50 são de grandes dimensões (portas, tejadilho, painéis inferior e laterais, entre outros) e necessitam, em média, de cinco ferramentas para o seu fabrico, sendo o custo estimado para cada ferramenta de 230 000 € [Col 2000, Alves 2003]. Para além da indústria automóvel, a conformação plástica de chapas metálicas é um processo tecnológico presente nas indústrias relativas à aeroespacial, petrolífera, decoração, alimentar, entre outras. Do ponto de vista do enquadramento económico, cerca de 20% do custo total de um automóvel novo é devido à incorporação de componentes metálicos estampados. [Alves 2003]. A pressão do “Mercado Global” faz com que os custos relativos à matéria-prima, energia e mão-de-obra sejam uma constante em termos de redução do seu impacte no orçamento das empresas fornecedoras destes produtos. É neste contexto que surge a necessidade da realização deste estudo de Benchmark de Softwares, tornando-se bastante importante, quer ao nível da competitividade industrial, quer ao nível da inovação para novos produtos. A análise por elementos finitos desempenha um papel primordial no tryout virtual e otimização das ferramentas e processos de conformação plástica. Os objetivos principais deste estudo de simulação numérica são a identificação e comparação dos resultados obtidos pelo AUTOFORM e pelo PAMSTAMP, para cada uma das variáveis identificadas como as mais influentes na robustez dos processos de estampagem de chapa metálica. Estas variáveis identificadas são: consumo de material (Draw-in) após conformação; forças de conformação; valores de variação de espessura e dos valores de extensão e resultados de Springback. Os resultados obtidos são comparados com os resultados experimentais e, desta forma, avalia-se a capacidade inovadora e a eficácia de cada um dos softwares, obtendo-se assim, uma orientação mais real para o software mais indicado aos objetivos impostos pela indústria automóvel. Para este efeito, a indústria automóvel, como maior impulsionador e motor da investigação na área da simulação numérica aplicada aos processos de estampagem, tem aderido em peso ao Benchmarking. Um exemplo disto, é o que acontece nas conferências Numisheet. O Benchmark #2 da conferência Numisheet 2008 é analisado pormenorizadamente e os resultados numéricos e experimentais são comparados e apresentados. Dois materiais distintos (aço HC260LAD e liga de alumínio AC170), assim como três modelos com geometrias diferentes (com e sem freios) são apresentados neste relatório. Com vista à redução dos ciclos tentativa-erro, tem-se adotado ciclos virtuais ou numéricos e tem-se incrementado a interatividade entre as fases de concepção e projeto, num conceito muito próprio, mas cada vez mais abrangente, denominado “produção virtual”. É nesta filosofia que se insere a simulação numérica dos processos de conformação de chapa.

Lappeenrannan teknillisen yliopiston sähkötekniikan osaston uuden kaksivaiheisen tutkintorakenteen kansainvälinen vertailu. Raportti vertailuhankkeen toisesta vaiheesta 15.2.2005

Raportti käsittelee Lappeenrannan teknillisen yliopiston sähkötekniikan uutta kaksivaiheista tutkintorakennetta suhteessa ulkomaisiin vastaaviin master-tasoisiin tutkintorakenteisiin. Tutkimusmenetelmänä käytetään benchmarking-menetelmää. Tutkimusainesto kerätttiin 52:n eurooppalaisen yliopiston www-sivuilta ja opinto-oppaista. Näistä yliopistoista valittiin tarkempaan vertailuun kolme mielenkiintoiseksi vertailukumppaniksi valittua sähkötekniikan koulutusyksikköä: TUL, Technical University of Lodz, Puolasta. TUM,Technical University of München, Saksasta. KTH, Kungliga Tekniska Högskolan, Ruotsi. Toisen vaiheen vertailutulosten valossa näyttää siltä, että kaikkien vertailtujen yliopistojen tutkintojen sisällöt ja määrät ovat samankaltaisia, joten vertailukumppanit oletettavasti kykenevät ymmärtämään eri yliopistojen koulutusohjelmien toteutuksia. Toisaalta sähkötekniikan koulutuksen toteutukset näyttävät vertailuissa yliopistoissa sen verran erilaisilta, että vertailun avulla on mahdollista oppia eri toteutuksien taustalla olevista kulttuurieroista ja tavoitteista, sekä päästä hedelmälliseen yhteistyöhön vertailtavien yliopistojen sähkötekniikan osastojen kanssa.

Launch communications best practices: Online newspaper paywall context

The goal of the thesis is to identify the best practices of marketing communications in the context of online newspaper paywall launch. Theoretical point of views emphasize the value for the customer as an antecedent for a workable value proposition and marketing communications. Value-based communications contribute to the customer loyalty. The empirical evidence for this benchmark study was collected in seven company interviews. These firms represented several kinds of Finnish newspaper companies which had recently gone through the paywall launch and launch communications process. The results imply that there are multiple factors influencing on launch communications choices. However, recommendations can be drawn based on the common practices. The main managerial results were that the companies should utilize the online newspaper content and usage value as the core of the launch message, target both new and current readers and use multiple online and offline communications channels to reach the target audience. The launch communications message should be started with the emotional appeal, complemented with the more informative message later.

Lisäävän valmistuksen tarpeen kartoitus Kaakkois-Suomessa

Lisäävä valmistus (additive manufacturing, AM) on nykyaikainen menetelmä teollisuuskäyttöön tarkoitettujen kappaleiden valmistukseen. Vaikka Suomessa on vahva tieto lisäävästä valmistuksesta ja tutkimusta tehdään aktiivisesti, on menetelmän käyttö teollisuudessa vielä vähäistä. Tämän diplomityön tarkoituksena on kerätä tietoa kiinnostuksesta lisäävään valmistukseen Kaakkois-Suomen alueen yrityksiltä, jotka tekniikkaa voisivat hyödyntää. Työn tarkoituksena on myös tutkia vaatimuksia käyttöönotolle ja käyttökohteiden mahdollisuuksia Kaakkois-Suomen alueella. Työn tuloksena voidaan todeta, että kaksi syytä, jotka hidastavat lisäävän valmistuksen käyttöönottoa teollisuudessa, ovat ennakkoluulot teknologiaa kohtaan sekä perustiedon puuttuminen. Median luoma 3D-innostus luo myös paljon väärinkäsityksiä. Kaikesta huolimatta Kaakkois-Suomen alueen paperiteollisuudesta lähtenyt korkeatasoinen teollisuus- ja konepajaosaaminen pystyy toimimaan perustana teknologian käyttöönotolle.

Desarrollo de un modelo de evaluación de ciudades basado en el concepto de ciudad inteligente (Smart city)

La presente tesis tiene por finalidad contribuir al conocimiento de los procesos de transformación de las ciudades convencionales en Ciudades Inteligentes o Smart Cities, el nuevo paradigma urbano, que surge como consecuencia de la utilización de las Tecnologías de la Información y de las Comunicaciones, las TIC, para mejorar la calidad de vida de las personas y aumentar la eficiencia y eficacia de los procesos, servicios e infraestructuras de la ciudad. El proceso de urbanización de la población mundial constituye una de las principales tendencias globales. Los retos a los que se enfrentan las urbes actuales para satisfacer las necesidades de sus habitantes, así como la forma en que cada ciudad aborda dichos retos, propician el desarrollo de estudios comparativos y rankings de ciudades. La oportunidad para llevar a cabo esta tesis deriva de: La novedad del concepto de Ciudad Inteligente. La necesidad de establecer estudios comparativos, respecto a dicho concepto, entre ciudades con características socioeconómicas y culturales comunes, dado que la mayoría de los estudios y rankings se desarrollan para conjuntos de ciudades cuyas características son muy dispares, pues, en general son seleccionadas por su condición de capitales de estados o de centros económicos-financieros. El interés de disponer de estudios sobre ciudades con tamaños de población medianos, inferiores al millón de habitantes, las cuales tienen baja presencia en los estudios comparativos. La inexistencia de estudios comparativos entre las ciudades españolas, en relación con el concepto de Ciudad Inteligente. La existencia de la Red Española de Ciudades Inteligentes, que permite disponer de una muestra de ciudades adecuada, para llevar a cabo un estudio comparativo de acuerdo con los puntos anteriores. El objetivo general de la presente tesis es contribuir al conocimiento de los procesos de transformación de la ciudad convencional en Ciudad Inteligente, a través de la formulación y aplicación de un modelo de evaluación, basado en el concepto holístico de Ciudad Inteligente o Smart City y desde la perspectiva del ciudadano. La metodología de trabajo seguida comprende, en primer lugar, la revisión del estado del arte, centrada en tres aspectos: la evolución del concepto Smart City, los estudios comparativos sobre Ciudades Inteligentes y las medidas que las ciudades españolas están implantando en la práctica para llevar a cabo su transformación en Ciudades Inteligentes. A continuación se lleva a cabo el diseño el modelo de evaluación. Este modelo refleja el carácter holístico del concepto de Ciudad Inteligente, para lo cual, de acuerdo con las definiciones que encontramos en la literatura, evalúa la situación de cada ciudad en relación con seis ejes o pilares, comúnmente aceptados por los diferentes autores: e-Gobierno y e-Gobernanza, Movilidad, Sostenibilidad Ambiental, Desarrollo Económico, Capital Intelectual y Calidad de Vida. El trabajo desarrollado implica un análisis, que se desarrolla de forma ordenada para cada uno de los ejes y, dentro de éstos, para sus correspondientes factores. En total se analizan 18 factores. Para cada uno de los ejes se lleva a cabo una revisión de las iniciativas más representativas para, a continuación, analizar y evaluar los correspondientes los factores. De forma complementaria al desarrollo del trabajo, se llevó a cabo una encuesta, dirigida a profesionales de diferentes áreas y sectores, todos ellos en el ámbito de las Ciudades Inteligentes. El objetivo de la encuesta es conocer, de acuerdo con la opinión de los profesionales, la situación actual en materia de despliegue de Ciudades Inteligentes, las actuaciones que consideran de mayor interés para la ciudad y las barreras del proceso de cambio. Una vez definido el modelo, se ha aplicado a las 62 ciudades que forman la Red Española de Ciudades Inteligentes (RECI), valorando los factores y los ejes para cada una de ellas. Así mismo, se ha analizado la influencia de las tres variables siguientes: tamaño de población, densidad de población y presupuesto municipal por habitante, determinando la relación entre el porcentaje de ciudades inteligentes de la muestra, en cada factor. Adicionalmente en el eje Capital Intelectual,se analizó la influencia del porcentaje de habitantes con estudios superiores. Las 62 ciudades RECI que componen la muestra evaluada, representan el 43 % de las ciudades españolas que cuentan con poblaciones superiores a los 50.000 habitantes. La población que abarca la muestra de ciudades estudiada representa el 35% de la población española. Finalmente, se ha determinado el ranking con las ciudades de RECI, de acuerdo con el modelo diseñado. Así mismo se ha llevado a cabo el análisis de sensibilidad, determinado el ranking resultante para la misma muestra de ciudades, aplicando la ponderación de los factores. Las principales aportaciones de la tesis son: Desarrollar un modelo de evaluación de ciudades basada en el concepto holístico de la Smart City y desde la perspectiva del ciudadano. Desarrollar una metodología de trabajo fundamentada en el análisis sistematizado de las web municipales, como medio para conocer la situación de las ciudades, en lugar de los datos estadísticos publicados, que son la fuente de información habitualmente empleada en los estudios comparativos. Disponer de un estudio comparativo específico de ciudades españolas. Llevar a cabo un estudio sobre una muestra de ciudades de tamaño medio, con características socioeconómicas y culturales comparables. Mejorar el conocimiento de los procesos que se están llevando a cabo en ciudades con poblaciones inferiores al millón de habitantes. The purpose of this thesis is to contribute to the knowledge of the cities and the transformation that is taking part in traditional cities becoming Smart Cities. The Smart City concept is the new urban paradigm that is born from the extensive use of Information Technologies (IT) in order to accomplish better citizen’s quality of life as well as improvements in urban processes, services and infrastructures. Several rankings and benchmarking studies are being conducted globally, in response to the increasing of urban population that is taking part around the world and the subsequent challenges to be confronted by the cities. This thesis aims to contribute to these studies. The opportunity for this thesis comes from: The Smart City concept as a new concept. The need of benchmarking studies focused on the Smart City concept, carried on cities with similar social and economic characteristics. The interest on benchmarking studies on medium size cities (with less than one million inhabitants). The absence of benchmarking studies on Spanish cities. The existence of the Spanish Smart Cities Network that can be considered an appropriate sample for a benchmark study. The main goal of this thesis is to develop a Smart Cities assessment model based on the citizen point of view and taking into account a holistic concept of Smart City. The thesis methodology starts with the state of the art revision, focused on three items: the Smart City concept, the benchmark studies and the projects actually developed by the Spanish cities under processes for becoming Smart Cities. The next step is the assessment model design, in accordance with the six main axes or pillars referred in the academic literature: e-Government and e-Governance, Mobility, Environmental Sustainability, Economic Development, Smart Citizens and Quality of Life. Also, a survey has been conducted and addressed to experts working on the different areas related to the Smart Cities. The aim of this survey is to know their opinion about the deployment of the Smart Cities, the priorities considered by the cities and the barriers that delay the change processes. Once the assessment model was ready, it was applied to the Spanish Smart Cities Network, with 62 member cities. Also, the bearing of three variables: city population, population density and city budget per inhabitant, are studied. The 62 cities studied are 43 % of the Spanish cities with population over 50.000 inhabitants. The population living in these cities is the 35% of total Spanish population. The main contribution of this thesis are: An assessment model for Smart Cities that takes into account the holistic concept of the Smart City as well as the citizen experience. A methodology that comprises municipal web analysis instead of statistics data, which are the usual source of data for current benchmarking studies. A Spanish Smart Cities benchmark. A benchmark on medium size cities with similar social and economic characteristics. A better understanding of the urban processes that are taking part on cities under one million inhabitants.

Exploratory data analysis with non-linear and missing data in geochemistry

Exploratory analysis of data seeks to find common patterns to gain insights into the structure and distribution of the data. In geochemistry it is a valuable means to gain insights into the complicated processes making up a petroleum system. Typically linear visualisation methods like principal components analysis, linked plots, or brushing are used. These methods can not directly be employed when dealing with missing data and they struggle to capture global non-linear structures in the data, however they can do so locally. This thesis discusses a complementary approach based on a non-linear probabilistic model. The generative topographic mapping (GTM) enables the visualisation of the effects of very many variables on a single plot, which is able to incorporate more structure than a two dimensional principal components plot. The model can deal with uncertainty, missing data and allows for the exploration of the non-linear structure in the data. In this thesis a novel approach to initialise the GTM with arbitrary projections is developed. This makes it possible to combine GTM with algorithms like Isomap and fit complex non-linear structure like the Swiss-roll. Another novel extension is the incorporation of prior knowledge about the structure of the covariance matrix. This extension greatly enhances the modelling capabilities of the algorithm resulting in better fit to the data and better imputation capabilities for missing data. Additionally an extensive benchmark study of the missing data imputation capabilities of GTM is performed. Further a novel approach, based on missing data, will be introduced to benchmark the fit of probabilistic visualisation algorithms on unlabelled data. Finally the work is complemented by evaluating the algorithms on real-life datasets from geochemical projects.

Conceptual framework and pilot study to benchmark phylogenomic databases based on reference gene trees.

Phylogenomic databases provide orthology predictions for species with fully sequenced genomes. Although the goal seems well-defined, the content of these databases differs greatly. Seven ortholog databases (Ensembl Compara, eggNOG, HOGENOM, InParanoid, OMA, OrthoDB, Panther) were compared on the basis of reference trees. For three well-conserved protein families, we observed a generally high specificity of orthology assignments for these databases. We show that differences in the completeness of predicted gene relationships and in the phylogenetic information are, for the great majority, not due to the methods used, but to differences in the underlying database concepts. According to our metrics, none of the databases provides a fully correct and comprehensive protein classification. Our results provide a framework for meaningful and systematic comparisons of phylogenomic databases. In the future, a sustainable set of 'Gold standard' phylogenetic trees could provide a robust method for phylogenomic databases to assess their current quality status, measure changes following new database releases and diagnose improvements subsequent to an upgrade of the analysis procedure.

Findings of the standard benchmark library study group /

Includes bibliographical references.