Nonpoint source pollution, space, time and asymetric information - a deposit refund approach

The incorporation of space allows the establishment of a more precise relationship between a contaminating input, a contaminating byproduct and emissions that reach the final receptor. However, the presence of asymmetric information impedes the implementation of the first-best policy. As a solution to this problem a site specific deposit refund system for the contaminating input and the contaminating byproduct are proposed. Moreover, the utilization of a successive optimization technique first over space and second over time enables definition of the optimal intertemporal site specific deposit refund system

Finite field treatment of vibrational polarizabilities and hyperpolarizabilities: on the role of the Eckart conditions, their implementation, and their use in characterizing key vibrations

In the finite field (FF) treatment of vibrational polarizabilities and hyperpolarizabilities, the field-free Eckart conditions must be enforced in order to prevent molecular reorientation during geometry optimization. These conditions are implemented for the first time. Our procedure facilities identification of field-induced internal coordinates that make the major contribution to the vibrational properties. Using only two of these coordinates, quantitative accuracy for nuclear relaxation polarizabilities and hyperpolarizabilities is achieved in π-conjugated systems. From these two coordinates a single most efficient natural conjugation coordinate (NCC) can be extracted. The limitations of this one coordinate approach are discussed. It is shown that the Eckart conditions can lead to an isotope effect that is comparable to the isotope effect on zero-point vibrational averaging, but with a different mass-dependence

Supervisory systems in waste water treatment plants: sistematise their implementation

La implantació de Sistemes de Suport a la presa de Decisions (SSD) en Estacions Depuradores d'Aigües Residuals Urbanes (EDAR) facilita l'aplicació de tècniques més eficients basades en el coneixement per a la gestió del procés, assegurant la qualitat de l'aigua de sortida tot minimitzant el cost ambiental de la seva explotació. Els sistemes basats en el coneixement es caracteritzen per la seva capacitat de treballar amb dominis molt poc estructurats, i gran part de la informació rellevant de tipus qualitatiu i/o incerta. Precisament aquests són els trets característics que es poden trobar en els sistemes biològics de depuració, i en conseqüència en una EDAR. No obstant, l'elevada complexitat dels SSD fa molt costós el seu disseny, desenvolupament i aplicació en planta real, pel que resulta determinant la generació d'un protocol que faciliti la seva exportació a EDARs de tecnologia similar. L'objectiu del present treball de Tesi és precisament el desenvolupament d'un protocol que faciliti l'exportació sistemàtica de SSD i l'aprofitament del coneixement del procés prèviament adquirit. El treball es desenvolupa en base al cas d'estudi resultant de l'exportació a l'EDAR Montornès del prototipus original de SSD implementat a l'EDAR Granollers. Aquest SSD integra dos tipus de sistemes basats en el coneixement, concretament els sistemes basats en regles (els quals són programes informàtics que emulen el raonament humà i la seva capacitat de solucionar problemes utilitzant les mateixes fonts d'informació) i els sistemes de raonament basats en casos (els quals són programes informàtics basats en el coneixement que volen solucionar les situacions anormals que pateix la planta en el moment actual mitjançant el record de l'acció efectuada en una situació passada similar). El treball està estructurat en diferents capítols, en el primer dels quals, el lector s'introdueix en el món dels sistemes de suport a la decisió i en el domini de la depuració d'aigües. Seguidament es fixen els objectius i es descriuen els materials i mètodes utilitzats. A continuació es presenta el prototipus de SSD desenvolupat per la EDAR Granollers. Una vegada el prototipus ha estat presentat es descriu el primer protocol plantejat pel mateix autor de la Tesi en el seu Treball de Recerca. A continuació es presenten els resultats obtinguts en l'aplicació pràctica del protocol per generar un nou SSD, per una planta depuradora diferent, partint del prototipus. L'aplicació pràctica del protocol permet l'evolució del mateix cap a un millor pla d'exportació. Finalment, es pot concloure que el nou protocol redueix el temps necessari per realitzar el procés d'exportació, tot i que el nombre de passos necessaris ha augmentat, la qual cosa significa que el nou protocol és més sistemàtic.

Implementation and application of basis set superposition error-correction schemes to the theoretical modeling of weak intermolecular interactions

This thesis deals with the so-called Basis Set Superposition Error (BSSE) from both a methodological and a practical point of view. The purpose of the present thesis is twofold: (a) to contribute step ahead in the correct characterization of weakly bound complexes and, (b) to shed light the understanding of the actual implications of the basis set extension effects in the ab intio calculations and contribute to the BSSE debate. The existing BSSE-correction procedures are deeply analyzed, compared, validated and, if necessary, improved. A new interpretation of the counterpoise (CP) method is used in order to define counterpoise-corrected descriptions of the molecular complexes. This novel point of view allows for a study of the BSSE-effects not only in the interaction energy but also on the potential energy surface and, in general, in any property derived from the molecular energy and its derivatives A program has been developed for the calculation of CP-corrected geometry optimizations and vibrational frequencies, also using several counterpoise schemes for the case of molecular clusters. The method has also been implemented in Gaussian98 revA10 package. The Chemical Hamiltonian Approach (CHA) methodology has been also implemented at the RHF and UHF levels of theory for an arbitrary number interacting systems using an algorithm based on block-diagonal matrices. Along with the methodological development, the effects of the BSSE on the properties of molecular complexes have been discussed in detail. The CP and CHA methodologies are used for the determination of BSSE-corrected molecular complexes properties related to the Potential Energy Surfaces and molecular wavefunction, respectively. First, the behaviour of both BSSE-correction schemes are systematically compared at different levels of theory and basis sets for a number of hydrogen-bonded complexes. The Complete Basis Set (CBS) limit of both uncorrected and CP-corrected molecular properties like stabilization energies and intermolecular distances has also been determined, showing the capital importance of the BSSE correction. Several controversial topics of the BSSE correction are addressed as well. The application of the counterpoise method is applied to internal rotational barriers. The importance of the nuclear relaxation term is also pointed out. The viability of the CP method for dealing with charged complexes and the BSSE effects on the double-well PES blue-shifted hydrogen bonds is also studied in detail. In the case of the molecular clusters the effect of high-order BSSE effects introduced with the hierarchical counterpoise scheme is also determined. The effect of the BSSE on the electron density-related properties is also addressed. The first-order electron density obtained with the CHA/F and CHA/DFT methodologies was used to assess, both graphically and numerically, the redistribution of the charge density upon BSSE-correction. Several tools like the Atoms in Molecules topologycal analysis, density difference maps, Quantum Molecular Similarity, and Chemical Energy Component Analysis were used to deeply analyze, for the first time, the BSSE effects on the electron density of several hydrogen bonded complexes of increasing size. The indirect effect of the BSSE on intermolecular perturbation theory results is also pointed out It is shown that for a BSSE-free SAPT study of hydrogen fluoride clusters, the use of a counterpoise-corrected PES is essential in order to determine the proper molecular geometry to perform the SAPT analysis.

Enhanced convolution approach for CAC in ATM networks, an analytical study and implementation

The characteristics of service independence and flexibility of ATM networks make the control problems of such networks very critical. One of the main challenges in ATM networks is to design traffic control mechanisms that enable both economically efficient use of the network resources and desired quality of service to higher layer applications. Window flow control mechanisms of traditional packet switched networks are not well suited to real time services, at the speeds envisaged for the future networks. In this work, the utilisation of the Probability of Congestion (PC) as a bandwidth decision parameter is presented. The validity of PC utilisation is compared with QOS parameters in buffer-less environments when only the cell loss ratio (CLR) parameter is relevant. The convolution algorithm is a good solution for CAC in ATM networks with small buffers. If the source characteristics are known, the actual CLR can be very well estimated. Furthermore, this estimation is always conservative, allowing the retention of the network performance guarantees. Several experiments have been carried out and investigated to explain the deviation between the proposed method and the simulation. Time parameters for burst length and different buffer sizes have been considered. Experiments to confine the limits of the burst length with respect to the buffer size conclude that a minimum buffer size is necessary to achieve adequate cell contention. Note that propagation delay is a no dismiss limit for long distance and interactive communications, then small buffer must be used in order to minimise delay. Under previous premises, the convolution approach is the most accurate method used in bandwidth allocation. This method gives enough accuracy in both homogeneous and heterogeneous networks. But, the convolution approach has a considerable computation cost and a high number of accumulated calculations. To overcome this drawbacks, a new method of evaluation is analysed: the Enhanced Convolution Approach (ECA). In ECA, traffic is grouped in classes of identical parameters. By using the multinomial distribution function instead of the formula-based convolution, a partial state corresponding to each class of traffic is obtained. Finally, the global state probabilities are evaluated by multi-convolution of the partial results. This method avoids accumulated calculations and saves storage requirements, specially in complex scenarios. Sorting is the dominant factor for the formula-based convolution, whereas cost evaluation is the dominant factor for the enhanced convolution. A set of cut-off mechanisms are introduced to reduce the complexity of the ECA evaluation. The ECA also computes the CLR for each j-class of traffic (CLRj), an expression for the CLRj evaluation is also presented. We can conclude that by combining the ECA method with cut-off mechanisms, utilisation of ECA in real-time CAC environments as a single level scheme is always possible.

Integration of knowledge-based, qualitative and numeric tools for real time dynamic systems supervision

The proposal presented in this thesis is to provide designers of knowledge based supervisory systems of dynamic systems with a framework to facilitate their tasks avoiding interface problems among tools, data flow and management. The approach is thought to be useful to both control and process engineers in assisting their tasks. The use of AI technologies to diagnose and perform control loops and, of course, assist process supervisory tasks such as fault detection and diagnose, are in the scope of this work. Special effort has been put in integration of tools for assisting expert supervisory systems design. With this aim the experience of Computer Aided Control Systems Design (CACSD) frameworks have been analysed and used to design a Computer Aided Supervisory Systems (CASSD) framework. In this sense, some basic facilities are required to be available in this proposed framework: ·