This thesis presents experimental studies on the dissociative recombination (DR) of the organic molecular ions CD3CND+, CH2CHCNH+, CH3CH2CNH+, CD3CDO+, CH3CHO+ and DCOOD2+. The experiments were all performed at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. DR is the process in which a singly charged molecular cation captures a free electron, forming a highly excited intermediate molecule which then dissociates into exclusively neutral fragments. The process plays an important role as a plasma neutralizing mechanism in many cold, low density plasmas such as those encountered in planetary ionospheres and interstellar clouds. DR can also act as the final step in the gas-phase synthesis of different neutral molecules in such environments. Our experimental findings indicate that nitriles that are lost by protonation in Titan’s upper atmosphere or in interstellar clouds to a large extent may be recycled by DR. Also, it appears that the DR of nitrile ions does not break the C-N bond, which supports the hypothesis that nitriles which are formed in Titan’s upper atmosphere do not degrade to recover N2. For the studied acetaldehyde cations, CD3CDO+ and CH3CHO+, we observed a considerable isotopic effect in the cross section, with the lighter isotopologue being more reactive. In the DR of DCOOD2+ an upper limit of only 13% for the branching fraction of the DCOOD + D channel was found. This finding has pronounced effects on the predicted abundance of formic acid in dark clouds.

This thesis analyses and proposes solutions for the following PNe mysteries: 1. The missing PNe population. 100 new objects were spectroscopically observed and analysed using the INT Photometric Halpha Survey (IPHAS). 32 are PNe, 13 are possible PNe and the rest are HII regions, SNR and unclear objects. The new PNe were within the inner parts of the galactic plane. The IPHAS survey has been the deepest survey done in Halpha, and revealed objects never seen before. 2. The mixed chemistry in Galactic Bulge PNe. These GBPNe are the end-products of low-mass stars (and therefore expected to be O-rich) and belong to a metal rich population. These PNe present dual-dust chemistry, with the presence of PAHs (carbon-rich) and crystalline silicates (oxygen-rich) in their spectra. This thesis analysed 40 Galactic Bulge PNe and found a strong correlation between intensity of the PAH bands and morphology, notably a massive torus. This torus provides the dense irradiated environment needed to form the PAHs. Follow-up observations using VISIR revealed a dense dusty tori in 11 PNe. PAHs are present in the outer edges of these tori, whereas ionised material is located within the dusty tori.3. The 3He problem. Using the VLA we observed three PNe, upper-limits of their 3He abundances were estimated. The resulting evolution of 3He is only consistent with the values determined in pre-solar material and the ISM, if the PNe observed represent only 4% of the population of low-mass stars, and the remaining 96% have undergone enhanced 3He depletion.

No description available.

Context. Ammonia and its deuterated isotopologues probe physical conditions in dense molecular cloud cores. The time-dependence of deuterium fractionation and the relative abundances of different nuclear spin modifications are supposed to provide a means of determining the evolutionary stages of these objects. Aims. We aim to test the current understanding of spin-state chemistry of deuterated species by determining the abundances and spin ratios of NH2D, NHD2 and ND3 in a quiescent, dense cloud. Methods. Spectral lines of NH3, NH2D, NHD2, ND3 and N2D+ were observed towards a dense, starless core in Ophiuchus with the APEX, GBT and IRAM 30-m telescopes. The observations were interpreted using a gas-grain chemistry model combined with radiative transfer calculations. The chemistry model distinguishes between the different nuclear spin states of light hydrogen molecules, ammonia and their deuterated forms. Different desorption schemes can be considered. Results. High deuterium fractionation ratios with NH2D = NH3 similar to 0 : 4, NHD2 = NH2D similar to 0 : 2 and ND3 = NHD2 similar to 0 : 06 are found in the core. The observed ortho/para ratios of NH2D and NHD2 are close to the corresponding nuclear spin statistical weights. The chemistry model can approximately reproduce the observed abundances, but consistently predicts too low ortho/para-NH2D, and too large ortho/para-NHD2 ratios. The longevity of N2H+ and NH3 in dense gas, which is prerequisite to their strong deuteration, can be attributed to the chemical inertia of N-2 on grain surfaces. Conclusions. The discrepancies between the chemistry model and the observations are likely to be caused by the fact that the model assumes complete scrambling in principal gas-phase deuteration reactions of ammonia, which means that all the nuclei are mixed in reactive collisions. If, instead, these reactions occur through proton hop/hydrogen abstraction processes, statistical spin ratios are to be expected. The present results suggest that while the deuteration of ammonia changes with physical conditions and time, the nuclear spin ratios of ammonia isotopologues do not probe the evolutionary stage of a cloud.

Este trabalho apresenta o estudo de algumas moléculas do meio interestelar úteis para o levantamento do conteúdo de matéria orgânica do universo e para as condições pré-bióticas na Terra e em outros ambientes no universo. Utilizamos como objeto-teste a Nebulosa Cabeça de Cavalo, devido à sua geometria simples, à sua distância moderada até nós, ao seu campo de radiação ultravioleta bem conhecido resultante da iluminação por uma estrela próxima, $\\sigma$ Orionis, e por ter sido extensivamente estudada por diversos trabalhos. Desse modo, podemos investigar com segurança diversos processos físicos e químicos no meio interestelar. O principal instrumento utilizado neste trabalho foi o código PDR Meudon devido ao fato de que é amplamente utilizado por ser um dos programas de análise de dados de projetos recentes de astronomia, como o projeto Herschel, e por ser público. O código pode ser utilizado para modelizar com confiabilidade a Nebulosa Cabeça de Cavalo, visto que ela mesma é uma PDR (região de fotodissociação) prototípica. Atualizamos o setor de química do código para testar diversos cenários de formação de moléculas. Consideramos o impacto nas abundâncias derivadas das moléculas de várias suposições em relação ao estado do gás (modelos isocórico, isotérmico e isobárico), decidindo em favor de um modelo isobárico. Verificou-se o papel dos raios cósmicos e de vários conjuntos de dados das reações químicas. Obtivemos as abundâncias de várias moléculas, incluindo algumas de potencial importância pré-biótica: CN e seus íons, HCN, HNC, nitrilas e seus íons, hidretos de nitrogênio, benzeno. Investigamos o papel dos ânions e dos PAHs. Finalmente, exploramos canais de produção para heterocíclicos nitrogenados com relevância em astrobiologia: pirrol e piridina. As presentes simulações apresentaram como a exploração de uma pequena gama de possíveis canais de produção de heterocíclicos já resultou em abundâncias significativas para ao menos uma espécie de heterocíclicos nitrogenados, a piridina. Dessa forma, excursões sistemáticas pelos diversos canais de produção deverão revelar mais espécies para serem alvos de buscas. / This work presents the study of some molecules of the interstellar medium that are useful for the bookkeeping of the molecular content of the universe and for prebiotic conditions on Earth and in other environments in the universe. The Horsehead Nebula was chosen as test object, due to its simple geometry, its moderate distance to us, its well-known ultraviolet radiation field resulting from the star $\\sigma$ Orionis, and due the fact that it has been extensively studied in several works. In this way, we can safely investigate several physical and chemical processes on the interstellar medium. The main tool used in the present work was the Meudon PDR code due the fact that it is widely used as one of the legacy data analysis programs of current astronomy projects, e.g. the Herschel project, and it is public. The code can reliably model the Horsehead Nebula, since this nebula is a prototypic PDR (photodissociation region). We updated the chemical sector of the code in order to test several scenarios for molecule production. We considered the impact on the derived molecule abundances of several assumptions relative to the gas state (isochoric, isothermal and isobaric models), and the isobaric model was found to be the most plausible. We checked the role of cosmic rays and several datasets of chemical reactions. We derived the abundances of several molecules, including some of potential prebiotic importance: CN and their ions, HCN, HNC, nitriles and their ions, nitrogen hydrides, and benzene. We investigated the role of anions and PAHs. Finally, we explored production channels for astrobiologically relevant nitrogenated heterocycles: pyrrole and pyridine. This presents simulations show us how the exploration of a small quantities of possibles path of prodution of heterocycles resulted already in significants abundances at least one n-heterocycle specie, the pyridine. Thereby, systemact tours for the many productions paths should show more species to be targe of searches.

The calculation of the physical conditions near the inner rim of a protoplanetary disk using the new computational model Pisco is described. Diagnostic plots illustrate solutions for disk structure, radiation field, chemical composition, and heating and cooling of the disk in a steady-state approximation for both disks with unsettled dust and with settled dust. Disks with unsettled dust are found to have hotter gas temperatures above the disk photosphere and a more pronounced temperature inversion at the disk photosphere. Recommendations are made for the development of Pisco. Pisco has the potential to explore what observed molecular emission can imply about disk structure. / text

In this thesis the major work described concerns experimental determination of the dissociative recombination (DR) reaction for several molecular ions of astrochemical interest. DR is the process where an electron recombines with a molecular ion to form an excited neutral that disintegrates into two or more neutral fragments to release the gained excess energy. It is very efficient under cold conditions and therefore ubiquitously occurring in interstellar environments such as dark clouds and plays an important role in aeronomical plasmae, lightnings and in man-made plasmas such as in combustion engines and fusion reactors. Although DR reactions are crucial processes in all these environments, product branching fractions of DR reactions have proven to be very unpredictable and present one of the great remaining challenges for theoreticians. The experimental work includes determination of reaction rates and product distribution of DR of complex ions such as protonated alcohols and ethers. The following species have been investigated and are discussed in this thesis: CH3OH2+ (protonated methanol), CD3OD2+ (deuteronated methanol), CD3OCD2+ (methoxymethyl cation), CD3CDOD+ (deuteronated acetaldehyde), CH3CH2OH2+ (protonated ethanol) and (CD3)2OD+ (deuteronated dimethyl ether). The results of these measurements are used in astrochemical model calculations in which the rates used hitherto greatly have been based on educated guesses. Employing the outcome of the DR investigations of the CH3OH2+ and CD3OD2+ ions have shown a great impact on such models. The DR investigations have been followed up by astronomical observations. Theoretical models and laboratory experiments show that methanol should be formed from CO on cold grains. This scenario was tested by astronomical observations of gas associated with young stellar objects (YSOs). Two independent tests were showing consistency with methanol formation on grain surfaces. / I den här avhandlingen redovisas mitt arbete som till stor del baseras på experimentell bestämning av dissociativa rekombinations (DR) processer för molekylära joner av astrokemiskt intresse. DR är en process där en elektron rekombinerar med en molekylär jon som splittras up i två eller fler neutrala fragment för att göra sig av med den extra energi som erhållits. Processen är väldigt effektiv i kalla miljöer varför den är allestädes återkommande i omgivningar som interstellära moln och kometkoman och spelar en betydande roll i aeronomiska plasman, blixturladdningar men även i mänskligt skapade plasman såsom de i förbränningsmotorer och fusionsreaktorer. Det har dock visat sig att produkt distributionsförhållandena från DR reaktioner är mycket oförutsägbara och kvarstår som en av de stora återstående utmaningarna för teoretiker. Det experimentella arbetet består av bestämning av reaktionshastigheter samt produktdistribution för DR av komplexa joner som protonerade alkoholer och etrar. De följande jonerna har blivit undersökta och diskuteras i denna avhandling: CH3OH2+ (protonerad metanol), CD3OD2+ (deuteronerad metanol), CD3OCD2+ (metoxymetyl katjon), CD3CDOD+ (deuteronerad acetaldehyd), CH3CH2OH2+ (protonerad etanol) och (CD3)2OD+ (deuteronerad dimetyleter). Resultaten av mätningarna används i astrokemiska modelberäkningar i vilka reaktionshastigheterna som hittills använts till stor del baserats på kvalificerade gissningar. Insättning av resultaten av CH3OH2+ och CD3OD2+ jonerna har visat sig ha en stor effekt på sådana modeller. DR undersökningarna har följts upp av astronomiska observationer. Teoretiska modeller och laboratorieundersökningar visar att metanol borde kunna formas från CO på kalla iskornsytor, detta scenario har testats med astronomiska observationer av gas som associeras med unga stjärnor. Två oberoende undersökningar visade på förenlighet med metanolformation på kornytor. / At the time of the doctoral defense, the following papers were unpublished  and had a status as follows: Paper 1: Manuscript. Paper 2: In press. Paper 3: Manuscript. Paper 5: Manuscript.

Este trabalho apresenta o estudo de algumas moléculas do meio interestelar úteis para o levantamento do conteúdo de matéria orgânica do universo e para as condições pré-bióticas na Terra e em outros ambientes no universo. Utilizamos como objeto-teste a Nebulosa Cabeça de Cavalo, devido à sua geometria simples, à sua distância moderada até nós, ao seu campo de radiação ultravioleta bem conhecido resultante da iluminação por uma estrela próxima, $\\sigma$ Orionis, e por ter sido extensivamente estudada por diversos trabalhos. Desse modo, podemos investigar com segurança diversos processos físicos e químicos no meio interestelar. O principal instrumento utilizado neste trabalho foi o código PDR Meudon devido ao fato de que é amplamente utilizado por ser um dos programas de análise de dados de projetos recentes de astronomia, como o projeto Herschel, e por ser público. O código pode ser utilizado para modelizar com confiabilidade a Nebulosa Cabeça de Cavalo, visto que ela mesma é uma PDR (região de fotodissociação) prototípica. Atualizamos o setor de química do código para testar diversos cenários de formação de moléculas. Consideramos o impacto nas abundâncias derivadas das moléculas de várias suposições em relação ao estado do gás (modelos isocórico, isotérmico e isobárico), decidindo em favor de um modelo isobárico. Verificou-se o papel dos raios cósmicos e de vários conjuntos de dados das reações químicas. Obtivemos as abundâncias de várias moléculas, incluindo algumas de potencial importância pré-biótica: CN e seus íons, HCN, HNC, nitrilas e seus íons, hidretos de nitrogênio, benzeno. Investigamos o papel dos ânions e dos PAHs. Finalmente, exploramos canais de produção para heterocíclicos nitrogenados com relevância em astrobiologia: pirrol e piridina. As presentes simulações apresentaram como a exploração de uma pequena gama de possíveis canais de produção de heterocíclicos já resultou em abundâncias significativas para ao menos uma espécie de heterocíclicos nitrogenados, a piridina. Dessa forma, excursões sistemáticas pelos diversos canais de produção deverão revelar mais espécies para serem alvos de buscas. / This work presents the study of some molecules of the interstellar medium that are useful for the bookkeeping of the molecular content of the universe and for prebiotic conditions on Earth and in other environments in the universe. The Horsehead Nebula was chosen as test object, due to its simple geometry, its moderate distance to us, its well-known ultraviolet radiation field resulting from the star $\\sigma$ Orionis, and due the fact that it has been extensively studied in several works. In this way, we can safely investigate several physical and chemical processes on the interstellar medium. The main tool used in the present work was the Meudon PDR code due the fact that it is widely used as one of the legacy data analysis programs of current astronomy projects, e.g. the Herschel project, and it is public. The code can reliably model the Horsehead Nebula, since this nebula is a prototypic PDR (photodissociation region). We updated the chemical sector of the code in order to test several scenarios for molecule production. We considered the impact on the derived molecule abundances of several assumptions relative to the gas state (isochoric, isothermal and isobaric models), and the isobaric model was found to be the most plausible. We checked the role of cosmic rays and several datasets of chemical reactions. We derived the abundances of several molecules, including some of potential prebiotic importance: CN and their ions, HCN, HNC, nitriles and their ions, nitrogen hydrides, and benzene. We investigated the role of anions and PAHs. Finally, we explored production channels for astrobiologically relevant nitrogenated heterocycles: pyrrole and pyridine. This presents simulations show us how the exploration of a small quantities of possibles path of prodution of heterocycles resulted already in significants abundances at least one n-heterocycle specie, the pyridine. Thereby, systemact tours for the many productions paths should show more species to be targe of searches.

No description available.

It was once thought that molecules in the interstellar medium (ISM) would be destroyed in the harsh surroundings and conditions of space, and therefore unobservable by radio techniques. However, it is now understood that the chemistry of the ISM is vast and complex. The question still remains as to just how complex is this chemistry. Much is clearly still not understood. This dissertation presents work on the study of metal compounds and cations in the circumstellar envelopes of oxygen- and carbon-rich asymptotic giant branch (AGB) and supergiant stars. Laboratory studies were also conducted on several transition metal compounds of interstellar interest, some with high spin and orbital angular momentum states. Work has been completed to confirm the detection of the debated metal cyanide KCN in the carbon-rich AGB star IRC+10216. KCN joins the list as the fifth interstellar metal cyanide/isocyanide detected in this source. In addition, preliminary results on the search for TiO are presented towards the oxygen-rich supergiant star, VY CMa. To further understand the evolutionary processes of carbon- and oxygen-rich stars, a survey of HCO⁺ was taken towards the carbon star IRC+10216, the oxygen-rich AGBs TX Cam, IK Tau, and W Hya and the oxygen-rich supergiant NML Cyg. While HCO⁺ was detected towards all of these sources, the results vary. The outflow of NML Cyg proves to be asymmetric and further study is necessary. The emission from W Hya is significantly narrower than the other sources. The abundances of HCO⁺ in circumstellar gas increases inversely with mass-loss rate and ion-molecule chemistry appears to influence the chemistry of evolved circumstellar envelopes. To understand species in space with more confidence, a laboratory search for several 3d transition metal species of astrochemical interest was conducted in the laboratory: HZnCl (X¹∑⁺), ZnO (X¹∑⁺ and a³Πᵢ), ZnCl (X²∑⁺), TiS (X³Δᵣ) and CrS (X⁵Πᵣ). All of the molecules have been observed for the first time with high resolution gas phase rotational spectroscopy and the work on ZnO was the first gas-phase study of this molecule. Synthesis of the species required exotic production methods, including use of a DC discharge to produce all zinc species. By studying the rotational spectra, rest frequencies were determined that will be beneficial for future astronomical searches.