Intermolecular complexes between H₂O and atmospheric species HO, HO₂, H₂O₂, O₃, NO and NO₂ have been studied by ab initio molecular orbital methods. The studies have been performed to the MP2 theory level by using 4-31G, 6-31G, D95, 6-31G**, D95**, 6-311G**, 6-311+G**, 6-311++G**, 6-311+G(2d,lp) and 6-311+G(2d,2p) basis sets. The geometries were fully optimized. The vibrational frequencies were calculated. The Basis Set Superposition Error (BSSE) were estimated. Finally, the binding energies of the complexes were predicted with other thermochemical properties. The binding energies of H₂O•HO, H₂O•HO₂, H₂O•H₂O₂, H₂O•O₃, H₂O•NO and H₂O•NO₂ are estimated to be 5.7±0.6, 8.9±1.0, 7.3±1.3, 1.8±0.2, 1.17 (no BSSE correction) and 2.98 (no BSSE correction) Kcal/Mol, respectively. The Kcq for dimerization to yield H₂O•HO, H₂O•HF, H₂O•HO₂, H₂O•H₂O and H₂O•H₂O₂ are estimated to be 0.11, 2.8, 3.3, 0.067 and 0.11 atm¯¹, respectively. The H₂O•HO, H₂O•HF, H₂O•HO₂, H₂O•H₂O and H₂O•H₂O₂ are quite strongly bonded complexes, while H₂O•O₃, H₂O•NO and H₂O•NO₂ are only weakly bonded complexes. The Kcq changes with temperature are discussed, and their importance in atmospheric chemistry are addressed.

Resumo: A quantificação do vapor d'água integrado na atmosfera (IWV - Integrated Water Vapor), ao contrário de outras variáveis meteorológicas, é algo que ainda se apresenta como um grande desafio para as Ciências Atmosféricas. Diversos mecanismos, envolvendo diferentes técnicas, têm sido empregados e testados para esse fim em diferentes regiões do globo por pesquisa dores das mais variadas áreas da ciência. Essa tese apresenta uma contribuição a esse tema ao empregar receptores GPS (Global Positioning System) em bases terrestres, localizados no Brasil, envolvendo instituições de pesquisa na área de Geodésia e de Meteorologia. Os objetivos principais desse trabalho são validar os valores do IWV obtidos a partir das observações GPS e contribuir com a viabilização da utilização de redes ativas de receptores GPS, existentes atualmente e futuras, no monitoramento do IWV como suporte às atividades da Meteorologia e Climatologia no Brasil. Os resultados obtidos mostram que, com a efetivação desse processo, poderá ser obtida uma fonte adicional de informações da umidade para Previsão Numérica de Tempo (PNT). Além disso, é mostrado também que a alta resolução temporal dos valores do IWV obtidos a partir das observações GPS pode contribuir para a melhoria dos resultados gerados por outras técnicas empregadas na mesma tarefa. Em contrapartida, um modelo de PNT é utilizado para gerar previsões da influência da troposfera nos sinais GPS, visando beneficiar aplicações GPS em tempo real. Os resultados gerados nesse trabalho são frutos da sinergia entre as duas áreas envolvidas e mostram que, atualmente, há boas perspectivas para essa parceria no Brasil. / Abstract: Quantification of Integrated Water Vapor (IWV), unlike other meteorological variables, still represents a significant challenge to the Atmospheric Sciences. In this task several techniques using different mechanisms have been employed and tested in different regions of the planet. Many researchers from several areas of science have been involved in this process. This thesis presents a contribution to this theme, employing ground-based GPS receivers installed on Brazilian territory, involving Geodesy and Meteorology research institutes. The main aim of this work is to contribute in order to make enable the use of the existing networks of continuously operating GPS receivers, and those that will be installed in the future, in IWV monitoring to support meteorological and climatological activities in Brazil. The results generated show that in this process it is possible to obtain an additional source of humidity information for Numerical Weather Prediction (NWP). Furthermore, the prospect of using the ground-based GPS receivers to monitor atmospheric water vapor is promising because thehigh temporal resolution of IWV values from GPS observations can improve the results generated from other techniques employed in the same task. At the same time, a NWP model is applied to generate predictions of the atmosphere's influence over radiofrequency signals, to improve real time GPS applications. The results of this work stem from the synergy between the two areas of science involved. They show that the current outlook for this partnership in Brazil is good, and that both Meteorology and Geodesy will benefit. / Orientador: João Francisco Galera Monico / Coorientador: João Augusto Toledo Machado / Banca: José Antonio Aravequia / Banca: Paul J. de Jonge / Banca: José Tadeu Garcia Tommaselli / Banca: Paulo de Oliveira Camargo / Doutor

Made available in DSpace on 2014-06-11T19:31:04Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-12-07Bitstream added on 2014-06-13T20:01:31Z : No. of bitstreams: 1 sapucci_lf_dr_prud.pdf: 3782471 bytes, checksum: af4cccfc2f5cb3b6dd4ba86dfb21c180 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A quantificação do vapor d'água integrado na atmosfera (IWV - Integrated Water Vapor), ao contrário de outras variáveis meteorológicas, é algo que ainda se apresenta como um grande desafio para as Ciências Atmosféricas. Diversos mecanismos, envolvendo diferentes técnicas, têm sido empregados e testados para esse fim em diferentes regiões do globo por pesquisa dores das mais variadas áreas da ciência. Essa tese apresenta uma contribuição a esse tema ao empregar receptores GPS (Global Positioning System) em bases terrestres, localizados no Brasil, envolvendo instituições de pesquisa na área de Geodésia e de Meteorologia. Os objetivos principais desse trabalho são validar os valores do IWV obtidos a partir das observações GPS e contribuir com a viabilização da utilização de redes ativas de receptores GPS, existentes atualmente e futuras, no monitoramento do IWV como suporte às atividades da Meteorologia e Climatologia no Brasil. Os resultados obtidos mostram que, com a efetivação desse processo, poderá ser obtida uma fonte adicional de informações da umidade para Previsão Numérica de Tempo (PNT). Além disso, é mostrado também que a alta resolução temporal dos valores do IWV obtidos a partir das observações GPS pode contribuir para a melhoria dos resultados gerados por outras técnicas empregadas na mesma tarefa. Em contrapartida, um modelo de PNT é utilizado para gerar previsões da influência da troposfera nos sinais GPS, visando beneficiar aplicações GPS em tempo real. Os resultados gerados nesse trabalho são frutos da sinergia entre as duas áreas envolvidas e mostram que, atualmente, há boas perspectivas para essa parceria no Brasil. / Quantification of Integrated Water Vapor (IWV), unlike other meteorological variables, still represents a significant challenge to the Atmospheric Sciences. In this task several techniques using different mechanisms have been employed and tested in different regions of the planet. Many researchers from several areas of science have been involved in this process. This thesis presents a contribution to this theme, employing ground-based GPS receivers installed on Brazilian territory, involving Geodesy and Meteorology research institutes. The main aim of this work is to contribute in order to make enable the use of the existing networks of continuously operating GPS receivers, and those that will be installed in the future, in IWV monitoring to support meteorological and climatological activities in Brazil. The results generated show that in this process it is possible to obtain an additional source of humidity information for Numerical Weather Prediction (NWP). Furthermore, the prospect of using the ground-based GPS receivers to monitor atmospheric water vapor is promising because thehigh temporal resolution of IWV values from GPS observations can improve the results generated from other techniques employed in the same task. At the same time, a NWP model is applied to generate predictions of the atmosphere's influence over radiofrequency signals, to improve real time GPS applications. The results of this work stem from the synergy between the two areas of science involved. They show that the current outlook for this partnership in Brazil is good, and that both Meteorology and Geodesy will benefit.

Dans le contexte du réchauffement et du changement climatique, il est important d’étudier les distributions, les cycles saisonniers et les tendances des gaz à l’état de trace dans l’atmosphère tels que la vapeur d’eau. L'Observatoire de Physique du Globe de Clermont-Ferrand a en charge plusieurs dispositifs d’observation dont le site instrumenté Cézeaux, Opme et Puy de Dôme (CO-PDD) situés dans le centre de la France (45◦ N, 3◦ E). Le site des Cézeaux dispose d’un LIDAR Rayleigh – Mie - Raman fournissant en routine des profils verticaux de vapeur d’eau et de paramètres optiques caractérisant les cirrus. Le site du puy de Dôme est équipé d’un spectroscope à cavité optique (CRDS-Picarro). Des mesures de colonnes totales de vapeur d’eau sont disponibles sur tous ces sites par GPS. Le site d’Opme est équipé d’un pluviomètre. Enfin Météo-France effectue le travail de contrôle qualité des données météorologiques sur les stations de mesure en France et ces données ont été utilisées dans cette thèse. La validation des données sur le site du puy de Dôme a été la première la première exploitation dans cette thèse. Des comparaisons des données sur le puy de Dôme ont montré un très bon accord entre les données de vapeur d’eau extraites de la station météorologique du puy de Dôme, de Météo France et les donnes CRDS du puy de Dôme, avec une corrélation de 0.94 et 0.98 respectivement. Les profils verticaux obtenus par LIDAR ont permis de sélectionner une anomalie de vapeur d’eau et d’identifier une intrusion stratosphère-troposphère en analysant les processus dynamique associés à cette anomalie. Les données OLR ont montré que cette intrusion est accompagnée de convection profonde et enfin LACYTRAJ confirme l'origine stratosphérique d’une partie de la masse d'air présente au-dessus de Clermont-Ferrand au cours de l’anomalie. Les longues séries d’observations (ex : Puy de Dôme 1995-2015) et des ré-analyse ECMWF ERA-Interim (1979-2017) et la diversité des sources de données (ex : satellites AIRS et COSMIC), nous permettent de documenter, analyser et comparer la variabilité, les cycles et la tendance de la vapeur d'eau à la surface et dans la troposphère, à différentes échelles de temps et déterminer les processus géophysiques responsables des distributions de vapeur d'eau sur le site CO-PDD. Le cycle annuel de la vapeur d'eau est clairement établi pour les deux sites de différentes altitudes et pour tous les types de mesure. Les sites de Cézeaux et du puy de Dôme ne présentent presque aucun cycle diurne, suggérant que la variabilité de la vapeur d'eau à la surface sur ces deux sites est plus influencée par les systèmes météorologique sporadiques que par les variations diurnes régulières. Les données LIDAR montrent une plus grande variabilité mensuelle de la distribution verticale que les produits satellites COSMIC et AIRS. La colonne totale de vapeur d'eau GPS sur le site des Cézeaux présente une tendance positive (0,42 ± 0,45 g/kg*décade entre 2006-2017). L'analyse par régressions multi-linéaires montre que les forçages continentaux (East Atlantic, East Atlantic-West Russia) ont une plus grande influence que le forçage océanique (Nord Atlantic Oscillation) sur les variations de vapeur d'eau. / In the context of global warming and climate change, it is important to study the distributions, seasonal cycles and trends of trace gases in the atmosphere such as water vapor. of the Observatoire de Physique du Globe de Clermont-Ferrand is in charge of several observation devices including the instrumented site Cézeaux, Opme and Puy de Dôme (CO-PDD) located near the center of France (45◦ N, 3◦ E). The site of Cézeaux is instrumented by a Rayleigh - Mie–LIDAR Raman providing routine vertical profiles of water vapor mixing ratio and optical parameters characterizing cirrus clouds. The puy de Dôme site is equipped with an optical cavity spectroscope (CRDS-Picarro). Measurements of total water vapor columns are available on all these sites by GPS. The Opme site is equipped with rain gauges. Finally, Météo-France performs the quality control work and of data on meteorological stations in France and these data were used in this thesis. The validation of the puy de Dôme data was the first the first task in this thesis. Comparisons between the puy de Dôme data sets showed a very good agreement between the water vapor datafrom the OPGC meteorological station of Puy de Dôme, Météo France and CRDS data with a correlation of 0.94 and 0.98 respectively. The vertical profiles deduced from the LIDAR allowed to identify a water vapor anomaly and a stratosphere-troposphere intrusion associated with this anomaly. OLR data showed that this intrusion could be linked with deep convection and LACYTRAJ confirms the stratospheric origin of a part of the air mass present above Clermont-Ferrand. Long series of observations (eg Puy de Dôme 1995-2015) and ECMWF ERA-Interim re-analysis (1979-2017) and the diversity of data sources (eg AIRS and COSMIC satellites), allowed us to document, analyze and compare the variability, cycles and trend of surface and tropospheric water vapor at different time scales and determine the geophysical processes responsible for water vapor distributions at the site of CO-PDD. The annual cycle of water vapor is clearly established for the two sites of different altitudes and for all types of measurement. Cézeaux and puy de Dôme present almost no diurnal cycle, suggesting that the variability of surface water vapor at this site is more influenced by a sporadic meteorological system than by regular diurnal variations. The LIDAR dataset shows a greater monthly variability of the vertical distribution than the COSMIC and AIRS satellite products. The Cézeaux site presents a positive trend for the GPS water vapor total column (0.42 ± 0.45 g/kg*decade during 2006–2017) and a significant negative trend for the surface water vapor mixing ratio (−0.16 ± 0.09 mm/decade during 2002–2017). The multi-linear regression analysis shows that continental forcings (East Atlantic Pattern and East Atlantic-West Russia Pattern) have a larger influence than oceanic forcing (North Atlantic Oscillation) on the water vapor variations.