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.

Inclusão no Jardim de Infância : porta para o sucesso da inclusão no 1º ciclo

Este trabalho desenvolve-se no âmbito do mestrado em educação especial, domí-nio cognitivo e motor. Trata-se de um projeto de intervenção emergente do trabalho diário como educadora de infância, num agrupamento vertical de escolas que segue um modelo inclusivo. O projeto centrou-se numa aluna do pré-escolar em vias de ingressar no 1º ciclo e nas estratégias e atividades envolvidas na preparação e sucesso desse ingresso. Nesse sentido tornou-se necessário pesquisar sobre a problemática específica da aluna, sobre práticas inclusivas e sobre métodos e metodologias de intervenção. Isto é, investigou-se sobre paralisia cerebral, escola inclusiva, no modo como se podem articular estas duas questões, sobre pedagogia diferenciada e diferenciação pedagógica e ainda sobre as linhas de orientação para o pré-escolar e sobre as metas a atingir no fim desse ciclo. Desenvolveu-se um processo em que se utilizaram os procedimentos da investiga-ção/ação através de vários instrumentos (pesquisa documental, entrevista, testes sociomé-tricos e observação naturalista) a partir dos quais se elaborou um projeto que foi posto em prática ao longo do ano letivo de 2010/2011. Pode constatar-se no fim da intervenção que os resultados foram positivos, pois permitiram à aluna alcançar os objetivos inicialmente previstos, atingindo as metas da edu-cação pré-escolar e ingressar no 1º ciclo. Foram surgindo novas questões, entre elas a necessidade de promover de forma mais intensa a participação da família e a continuidade do trabalho desenvolvido após uma mudança de ciclo, e portanto, do grupo e dos professores.

Computer assisted instruction for developing speech perception skills in profoundly deaf children

This paper evaluates the usefulness of the "Foundations in Speech Perception" computer program developed by Breakthrough, Inc. in conjunction with Central Institute for the Deaf.

Developing a set of materials to teach hearing children about hearing impairment

This paper contains a set of materials to help hearing persons understand hearing loss.

Does systematic instruction in rhythmic movement influence the speech of the deaf

This paper discusses the influence of rhythm in teaching of hearing impaired children.

An analysis of the language of certain social study textbooks pertinent to instruction of deaf children

This paper discusses the results of a study of social studies textbooks suitable for hearing impaired children.

The effectiveness of phonics instruction for children with hearing impairments

This study reports the findings of a reading instruction survey of forty-five schools for the deaf across the United States.

A report on the language instruction provided to a group of deaf children

This paper is a summary of a course of language instruction provided to a group of deaf children over the course of one year.

The importance of direct language instruction for hearing impaired children

This paper discusses the importance of direct and intense language instruction for hearing impaired children in developing language and communication skills. The author presents a variety of activities for teacher use.

Evaluating lexically controlled word lists for open set speech perception testing in profoundly hearing impaired children

This paper evaluates speech perception testing in pediatric cochlear implant users. Using pre-recorded stimulus presentation, the author replicated an earlier experiment comparing the Lexical Neighborhood List (LNT) test to the Phonetically Balanced Kindergarten (PB-K) test in estimating speech perception abilities in hearing impaired children.

Open-set speech perception of school-age cochlear implant users

This study examines specific auditory features perceived by profoundly hearing-impaired children using conventional binaural hearing aids and the Nucleus 22 Channel Cochlear Implant. The primary interest of this study was to learn which speech features were most easily perceived by users of each device.

Reading instruction for hearing-impaired students in an auditory-oral setting

This paper discusses the instruction of reading for hearing impaired children.

A set of lectures concerning an educational approach towards the young hearing impaired child

This paper is a review of educational approaches for young hearing impaired children in South Africa.