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.

The potential of digital interactive television for the provision of healthcare and wellness services

The potential of digital interactive television (iDTV) to promote original services, formats and contents that can be relevant to support personal health care and wellness of individuals, namely elderly people, has not been yet fully explored in the past. Therefore, in a context of rapid change of the technological resources, in which the distribution and presentation of content comes associated with new platforms (such as digital terrestrial TV and IPTV), it is important to perceive the configurations that are being developed for interactive digital TV (iDTV) that may result in relevant outcomes within the field of healthcare and wellness, with the aim of offering complementarity to the existing services and contents made available today via the traditional means and media. This article describes and discusses the preliminary results of the first part of the research project iDTV-HEALTH: Inclusive services to promote health and wellness via digital interactive television. These first results suggest that iDTV solutions may represent a real contribution to delivery healthcare and wellness to the target population, namely as a supplement to health services provision.

Profiles of digital TV adopters in the switchover context in Portugal

In order to conduct a successful transition from analogue terrestrial television to full digital terrestrial television it is essential to identify what are the most significant drivers and barriers for adoption among the impacted population. Also importantly, it is to segment the population according with their attitudes towards digital TV, their awareness about the switchover process and intention of adopting digital TV, among other relevant topics. The tradition of profiles definition based on the adoption and rejection of innovations can be traced back to Beal & Bohlen, who proposed five categories of innovation adopters based on the time of adoption, with significant differences in selected personal and social characteristics: the innovators, the early adopters, the early majority, the majority and non-adopters. Later, Rogers would propose similar categories of adopters that became the standard for years to come: the innovators, the early adopters, the early majority, the late majority and the laggards. While helpful, these traditional innovation adopters’ profiles do not totally grasp the complexities of the adoption of an innovation such as digital TV, particularly in mandatory settings. In this paper we will propose a classification of adopters of digital TV in Portugal, based on the results of one of the four empirical studies of the research project ADOPT-DTV, namely, the quantitative inquiry administered to a representative sample of the Portuguese population. The paper will be concluded with a brief discussion of results and the enumeration of the next steps of the research project.

Incentives and Barriers to the Adoption of Digital Terrestrial Television in Portugal: Perspectives of the stakeholders involved in the transition process

The success of the transition from analogical terrestrial television to digital terrestrial television – process also known as switch-over – requires the identification of barriers and drivers among the impacted population. Therefore, the study in which this article is based had as main purpose to understand exactly what are those barriers, in order to produce a valid contribution to the several decision makers, and to be able to contribute to a more inclusive television, accessible and transversal to the whole of the population. In that sense, one of the phases of the project consisted in several interviews to key stakeholders in the transition process, the results of which and subsequent recommendations are presented in this article.

Analysis of return patterns of digital hearing aids

This paper examines the return rate for digital hearing aids and reason for the returns.

Analysis of return patterns of digital hearing aids

This paper examines the return rate for digital hearing aids and reason for the returns.

The use of digital technology for portfolio creation, management and utilization

The purpose of this study was to create a digital portfolio that was practical and effective for both teachers and parents.