Higher-order molecular properties and excitation energies in single-reference and multireference coupled-cluster theory

Coupled-cluster (CC) theory is one of the most successful approaches in high-accuracy quantum chemistry. The present thesis makes a number of contributions to the determination of molecular properties and excitation energies within the CC framework. The multireference CC (MRCC) method proposed by Mukherjee and coworkers (Mk-MRCC) has been benchmarked within the singles and doubles approximation (Mk-MRCCSD) for molecular equilibrium structures. It is demonstrated that Mk-MRCCSD yields reliable results for multireference cases where single-reference CC methods fail. At the same time, the present work also illustrates that Mk-MRCC still suffers from a number of theoretical problems and sometimes gives rise to results of unsatisfactory accuracy. To determine polarizability tensors and excitation spectra in the MRCC framework, the Mk-MRCC linear-response function has been derived together with the corresponding linear-response equations. Pilot applications show that Mk-MRCC linear-response theory suffers from a severe problem when applied to the calculation of dynamic properties and excitation energies: The Mk-MRCC sufficiency conditions give rise to a redundancy in the Mk-MRCC Jacobian matrix, which entails an artificial splitting of certain excited states. This finding has established a new paradigm in MRCC theory, namely that a convincing method should not only yield accurate energies, but ought to allow for the reliable calculation of dynamic properties as well. In the context of single-reference CC theory, an analytic expression for the dipole Hessian matrix, a third-order quantity relevant to infrared spectroscopy, has been derived and implemented within the CC singles and doubles approximation. The advantages of analytic derivatives over numerical differentiation schemes are demonstrated in some pilot applications.

Deep learning for computer vision: a comparison between convolutional neural networks and hierarchical temporal memories on object recognition tasks

In recent years, Deep Learning techniques have shown to perform well on a large variety of problems both in Computer Vision and Natural Language Processing, reaching and often surpassing the state of the art on many tasks. The rise of deep learning is also revolutionizing the entire field of Machine Learning and Pattern Recognition pushing forward the concepts of automatic feature extraction and unsupervised learning in general. However, despite the strong success both in science and business, deep learning has its own limitations. It is often questioned if such techniques are only some kind of brute-force statistical approaches and if they can only work in the context of High Performance Computing with tons of data. Another important question is whether they are really biologically inspired, as claimed in certain cases, and if they can scale well in terms of "intelligence". The dissertation is focused on trying to answer these key questions in the context of Computer Vision and, in particular, Object Recognition, a task that has been heavily revolutionized by recent advances in the field. Practically speaking, these answers are based on an exhaustive comparison between two, very different, deep learning techniques on the aforementioned task: Convolutional Neural Network (CNN) and Hierarchical Temporal memory (HTM). They stand for two different approaches and points of view within the big hat of deep learning and are the best choices to understand and point out strengths and weaknesses of each of them. CNN is considered one of the most classic and powerful supervised methods used today in machine learning and pattern recognition, especially in object recognition. CNNs are well received and accepted by the scientific community and are already deployed in large corporation like Google and Facebook for solving face recognition and image auto-tagging problems. HTM, on the other hand, is known as a new emerging paradigm and a new meanly-unsupervised method, that is more biologically inspired. It tries to gain more insights from the computational neuroscience community in order to incorporate concepts like time, context and attention during the learning process which are typical of the human brain. In the end, the thesis is supposed to prove that in certain cases, with a lower quantity of data, HTM can outperform CNN.

Fusion of probabilistic knowledge-based classification rules and learning automata for automatic recognition of digital images

In this paper, the fusion of probabilistic knowledge-based classification rules and learning automata theory is proposed and as a result we present a set of probabilistic classification rules with self-learning capability. The probabilities of the classification rules change dynamically guided by a supervised reinforcement process aimed at obtaining an optimum classification accuracy. This novel classifier is applied to the automatic recognition of digital images corresponding to visual landmarks for the autonomous navigation of an unmanned aerial vehicle (UAV) developed by the authors. The classification accuracy of the proposed classifier and its comparison with well-established pattern recognition methods is finally reported.

Prion crystalization model and its application to recognition pattern

This paper introduces APA (?Artificial Prion Assembly?): a pattern recognition system based on artificial prion crystalization. Specifically, the system exhibits the capability to classify patterns according to the resulting prion self- assembly simulated with cellular automata. Our approach is inspired in the biological process of proteins aggregation, known as prions, which are assembled as amyloid fibers related with neurodegenerative disorders.

Efficient Monte Carlo methods for multi-dimensional learning with classifier chains

Multi-dimensional classification (MDC) is the supervised learning problem where an instance is associated with multiple classes, rather than with a single class, as in traditional classification problems. Since these classes are often strongly correlated, modeling the dependencies between them allows MDC methods to improve their performance – at the expense of an increased computational cost. In this paper we focus on the classifier chains (CC) approach for modeling dependencies, one of the most popular and highest-performing methods for multi-label classification (MLC), a particular case of MDC which involves only binary classes (i.e., labels). The original CC algorithm makes a greedy approximation, and is fast but tends to propagate errors along the chain. Here we present novel Monte Carlo schemes, both for finding a good chain sequence and performing efficient inference. Our algorithms remain tractable for high-dimensional data sets and obtain the best predictive performance across several real data sets.

Application of PZT and FBG impedance sensors for structural health monitoring of reinforced concrete beams strengthened with FRP composite materials

Esta Tesis tiene como objetivo principal el desarrollo de métodos de identificación del daño que sean robustos y fiables, enfocados a sistemas estructurales experimentales, fundamentalmente a las estructuras de hormigón armado reforzadas externamente con bandas fibras de polímeros reforzados (FRP). El modo de fallo de este tipo de sistema estructural es crítico, pues generalmente es debido a un despegue repentino y frágil de la banda del refuerzo FRP originado en grietas intermedias causadas por la flexión. La detección de este despegue en su fase inicial es fundamental para prevenir fallos futuros, que pueden ser catastróficos. Inicialmente, se lleva a cabo una revisión del método de la Impedancia Electro-Mecánica (EMI), de cara a exponer sus capacidades para la detección de daño. Una vez la tecnología apropiada es seleccionada, lo que incluye un analizador de impedancias así como novedosos sensores PZT para monitorización inteligente, se ha diseñado un procedimiento automático basado en los registros de impedancias de distintas estructuras de laboratorio. Basándonos en el hecho de que las mediciones de impedancias son posibles gracias a una colocación adecuada de una red de sensores PZT, la estimación de la presencia de daño se realiza analizando los resultados de distintos indicadores de daño obtenidos de la literatura. Para que este proceso sea automático y que no sean necesarios conocimientos previos sobre el método EMI para realizar un experimento, se ha diseñado e implementado un Interfaz Gráfico de Usuario, transformando la medición de impedancias en un proceso fácil e intuitivo. Se evalúa entonces el daño a través de los correspondientes índices de daño, intentando estimar no sólo su severidad, sino también su localización aproximada. El desarrollo de estos experimentos en cualquier estructura genera grandes cantidades de datos que han de ser procesados, y algunas veces los índices de daño no son suficientes para una evaluación completa de la integridad de una estructura. En la mayoría de los casos se pueden encontrar patrones de daño en los datos, pero no se tiene información a priori del estado de la estructura. En este punto, se ha hecho una importante investigación en técnicas de reconocimiento de patrones particularmente en aprendizaje no supervisado, encontrando aplicaciones interesantes en el campo de la medicina. De ahí surge una idea creativa e innovadora: detectar y seguir la evolución del daño en distintas estructuras como si se tratase de un cáncer propagándose por el cuerpo humano. En ese sentido, las lecturas de impedancias se emplean como información intrínseca de la salud de la propia estructura, de forma que se pueden aplicar las mismas técnicas que las empleadas en la investigación del cáncer. En este caso, se ha aplicado un algoritmo de clasificación jerárquica dado que ilustra además la clasificación de los datos de forma gráfica, incluyendo información cualitativa y cuantitativa sobre el daño. Se ha investigado la efectividad de este procedimiento a través de tres estructuras de laboratorio, como son una viga de aluminio, una unión atornillada de aluminio y un bloque de hormigón reforzado con FRP. La primera ayuda a mostrar la efectividad del método en sencillos escenarios de daño simple y múltiple, de forma que las conclusiones extraídas se aplican sobre los otros dos, diseñados para simular condiciones de despegue en distintas estructuras. Demostrada la efectividad del método de clasificación jerárquica de lecturas de impedancias, se aplica el procedimiento sobre las estructuras de hormigón armado reforzadas con bandas de FRP objeto de esta tesis, detectando y clasificando cada estado de daño. Finalmente, y como alternativa al anterior procedimiento, se propone un método para la monitorización continua de la interfase FRP-Hormigón, a través de una red de sensores FBG permanentemente instalados en dicha interfase. De esta forma, se obtienen medidas de deformación de la interfase en condiciones de carga continua, para ser implementadas en un modelo de optimización multiobjetivo, cuya solución se haya por medio de una expansión multiobjetivo del método Particle Swarm Optimization (PSO). La fiabilidad de este último método de detección se investiga a través de sendos ejemplos tanto numéricos como experimentales. ABSTRACT This thesis aims to develop robust and reliable damage identification methods focused on experimental structural systems, in particular Reinforced Concrete (RC) structures externally strengthened with Fiber Reinforced Polymers (FRP) strips. The failure mode of this type of structural system is critical, since it is usually due to sudden and brittle debonding of the FRP reinforcement originating from intermediate flexural cracks. Detection of the debonding in its initial stage is essential thus to prevent future failure, which might be catastrophic. Initially, a revision of the Electro-Mechanical Impedance (EMI) method is carried out, in order to expose its capabilities for local damage detection. Once the appropriate technology is selected, which includes impedance analyzer as well as novel PZT sensors for smart monitoring, an automated procedure has been design based on the impedance signatures of several lab-scale structures. On the basis that capturing impedance measurements is possible thanks to an adequately deployed PZT sensor network, the estimation of damage presence is done by analyzing the results of different damage indices obtained from the literature. In order to make this process automatic so that it is not necessary a priori knowledge of the EMI method to carry out an experimental test, a Graphical User Interface has been designed, turning the impedance measurements into an easy and intuitive procedure. Damage is then assessed through the analysis of the corresponding damage indices, trying to estimate not only the damage severity, but also its approximate location. The development of these tests on any kind of structure generates large amounts of data to be processed, and sometimes the information provided by damage indices is not enough to achieve a complete analysis of the structural health condition. In most of the cases, some damage patterns can be found in the data, but none a priori knowledge of the health condition is given for any structure. At this point, an important research on pattern recognition techniques has been carried out, particularly on unsupervised learning techniques, finding interesting applications in the medicine field. From this investigation, a creative and innovative idea arose: to detect and track the evolution of damage in different structures, as if it were a cancer propagating through a human body. In that sense, the impedance signatures are used to give intrinsic information of the health condition of the structure, so that the same clustering algorithms applied in the cancer research can be applied to the problem addressed in this dissertation. Hierarchical clustering is then applied since it also provides a graphical display of the clustered data, including quantitative and qualitative information about damage. The performance of this approach is firstly investigated using three lab-scale structures, such as a simple aluminium beam, a bolt-jointed aluminium beam and an FRP-strengthened concrete specimen. The first one shows the performance of the method on simple single and multiple damage scenarios, so that the first conclusions can be extracted and applied to the other two experimental tests, which are designed to simulate a debonding condition on different structures. Once the performance of the impedance-based hierarchical clustering method is proven to be successful, it is then applied to the structural system studied in this dissertation, the RC structures externally strengthened with FRP strips, where the debonding failure in the interface between the FRP and the concrete is successfully detected and classified, proving thus the feasibility of this method. Finally, as an alternative to the previous approach, a continuous monitoring procedure of the FRP-Concrete interface is proposed, based on an FBGsensors Network permanently deployed within that interface. In this way, strain measurements can be obtained under controlled loading conditions, and then they are used in order to implement a multi-objective model updating method solved by a multi-objective expansion of the Particle Swarm Optimization (PSO) method. The feasibility of this last proposal is investigated and successfully proven on both numerical and experimental RC beams strengthened with FRP.

Computer methods for analysis and synthesis of visual texture,

"C00-2118-0048."

Bayesian methods for neural networks

Bayesian techniques have been developed over many years in a range of different fields, but have only recently been applied to the problem of learning in neural networks. As well as providing a consistent framework for statistical pattern recognition, the Bayesian approach offers a number of practical advantages including a potential solution to the problem of over-fitting. This chapter aims to provide an introductory overview of the application of Bayesian methods to neural networks. It assumes the reader is familiar with standard feed-forward network models and how to train them using conventional techniques.

Bayesian methods for neural networks

Bayesian techniques have been developed over many years in a range of different fields, but have only recently been applied to the problem of learning in neural networks. As well as providing a consistent framework for statistical pattern recognition, the Bayesian approach offers a number of practical advantages including a potential solution to the problem of over-fitting. This chapter aims to provide an introductory overview of the application of Bayesian methods to neural networks. It assumes the reader is familiar with standard feed-forward network models and how to train them using conventional techniques.

The use of multivariate methods in the identification of subtypes of Alzheimer's disease: a comparison of principal components and cluster analysis

Two contrasting multivariate statistical methods, viz., principal components analysis (PCA) and cluster analysis were applied to the study of neuropathological variations between cases of Alzheimer's disease (AD). To compare the two methods, 78 cases of AD were analyzed, each characterised by measurements of 47 neuropathological variables. Both methods of analysis revealed significant variations between AD cases. These variations were related primarily to differences in the distribution and abundance of senile plaques (SP) and neurofibrillary tangles (NFT) in the brain. Cluster analysis classified the majority of AD cases into five groups which could represent subtypes of AD. However, PCA suggested that variation between cases was more continuous with no distinct subtypes. Hence, PCA may be a more appropriate method than cluster analysis in the study of neuropathological variations between AD cases.

Applications of Nonclassical Logic Methods for Purposes of Knowledge Discovery and Data Mining

* The work is partially supported by Grant no. NIP917 of the Ministry of Science and Education – Republic of Bulgaria.

Projective Methods of Image Recognition

We propose a method for image recognition on the base of projections. Radon transform gives an opportunity to map image into space of its projections. Projection properties allow constructing informative features on the base of moments that can be successfully used for invariant recognition. Offered approach gives about 91-97% of correct recognition.

Digital anthropology and educational eGames: learning through behavioural patterns in digital, game-based contexts

The selected publications are focused on the relations between users, eGames and the educational context, and how they interact together, so that both learning and user performance are improved through feedback provision. A key part of this analysis is the identification of behavioural, anthropological patterns, so that users can be clustered based on their actions, and the steps taken in the system (e.g. social network, online community, or virtual campus). In doing so, we can analyse large data sets of information made by a broad user sample,which will provide more accurate statistical reports and readings. Furthermore, this research is focused on how users can be clustered based on individual and group behaviour, so that a personalized support through feedback is provided, and the personal learning process is improved as well as the group interaction. We take inputs from every person and from the group they belong to, cluster the contributions, find behavioural patterns and provide personalized feedback to the individual and the group, based on personal and group findings. And we do all this in the context of educational games integrated in learning communities and learning management systems. To carry out this research we design a set of research questions along the 10-year published work presented in this thesis. We ask if the users can be clustered together based on the inputs provided by them and their groups; if and how these data are useful to improve the learner performance and the group interaction; if and how feedback becomes a useful tool for such pedagogical goal; if and how eGames become a powerful context to deploy the pedagogical methodology and the various research methods and activities that make use of that feedback to encourage learning and interaction; if and how a game design and a learning design must be defined and implemented to achieve these objectives, and to facilitate the productive authoring and integration of eGames in pedagogical contexts and frameworks. We conclude that educational games are a resourceful tool to provide a user experience towards a better personalized learning performance and an enhance group interaction along the way. To do so, eGames, while integrated in an educational context, must follow a specific set of user and technical requirements, so that the playful context supports the pedagogical model underneath. We also conclude that, while playing, users can be clustered based on their personal behaviour and interaction with others, thanks to the pattern identification. Based on this information, a set of recommendations are provided Digital Anthropology and educational eGames 6 /216 to the user and the group in the form of personalized feedback, timely managed for an optimum impact on learning performance and group interaction level. In this research, Digital Anthropology is introduced as a concept at a late stage to provide a backbone across various academic fields including: Social Science, Cognitive Science, Behavioural Science, Educational games and, of course, Technology-enhance learning. Although just recently described as an evolution of traditional anthropology, this approach to digital behaviour and social structure facilitates the understanding amongst fields and a comprehensive view towards a combined approach. This research takes forward the already existing work and published research onusers and eGames for learning, and turns the focus onto the next step — the clustering of users based on their behaviour and offering proper, personalized feedback to the user based on that clustering, rather than just on isolated inputs from every user. Indeed, this pattern recognition in the described context of eGames in educational contexts, and towards the presented aim of personalized counselling to the user and the group through feedback, is something that has not been accomplished before.

Classificação de água de coco processada e natural por meio de HCA, PCA e teores de íons metálicos determinados por ICP OES

Inductively Coupled Plasma Optical Emission Spectrometry was used to determine Ca, Mg, Mn, Fe, Zn and Cu in samples of processed and natural coconut water. The sample preparation consisted in a filtration step followed by a dilution. The analysis was made employing optimized instrumental parameters and the results were evaluated using methods of Pattern Recognition. The data showed common concentration values for the analytes present in processed and natural samples. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) indicated that the samples of different kinds were statistically different when the concentrations of all the analytes were considered simultaneously.

25 anos de quimiometria no Brasil

Chemometric activities in Brazil are described according to three phases: before the existence of microcomputers in the 1970s, through the initial stages of microcomputer use in the 1980s and during the years of extensive microcomputer applications of the ´90s and into this century. Pioneering activities in both the university and industry are emphasized. Active research areas in chemometrics are cited including experimental design, pattern recognition and classification, curve resolution for complex systems and multivariate calibration. New trends in chemometrics, especially higher order methods for treating data, are emphasized.