Interstellar plasma — interstellar clouds in particular — play an important role in determining the structure and evolution of galaxies. Understanding the time evolution of such plasmas requires knowledge of the chemical processes that drive their dynamics. Two processes are studied in this dissertation: radiative electron attachment (REA) via dipole-bound states (DBSs) and dissociative recombination (DR). Of the several hundred molecules detected in the interstellar medium, only eight anions have been detected: CN-, C3N-, C5N-, C7N-, C4H-, C6H-, C8H-, and C10H-. Their production mechanism is not well known; REA was suggested as a possible formation pathway, but previous theoretical studies have found that REA rate coefficients were too low to explain the formation of CN-, C3N-, and C5N-. It was later suggested that including DBSs — an electron weakly bound at a large distance to the large dipole moment of a neutral molecule — could appreciably enhance the REA rate coefficients. The first portion of this study is dedicated to investigating the role of the large dipole moment of rotating C3N using an accurate \it ab initio approach with electronic and rotational resolution. DBS wavefunctions of C3N- are calculated and used to obtain REA cross sections that produce even smaller rate coefficients, suggesting that C3N- is efficiently formed by a different process. The second part of this study investigates DR in the difficult case of molecules with low-lying eletronic resonances, although these are not necessary for the approach. An approach to treat both direct and indirect mechanisms of DR in a diatomic ion with electronic, vibrational, and rotational resolution using R-matrix scattering calculations, frame transformation theory, and multichannel quantum defect theory is presented and applied to the CH+ and CF+ molecular ions at low collision energies. The calculated CH+ cross sections agree well with recent rotationally state-resolved experimental results and overall better than previous theoretical results. The calculated CF+ cross sections agree well with experimental results, although these do not have rotational resolution, and overall better than previous theoretical results at low energies. Additionally, the method can study rovibronic (de-)excitation — a process in competition with DR. These are calculated and compared to previous theoretical calculations for CH+, which which our results agree well with the exception of dipole-driven rotational excitation cross sections. This discrepancy is tentatively attibuted to negelcting the contribution of higher partial waves in the description of the incident electron, which will be incorporated in future studies.

L’étude des mécanismes de formation et de destruction des anions moléculaires est devenu un champ d’intérêt prononcé après la détection récente de six anions moléculaires (C4H-, C6H-, C8H-, CN-, C3N-, C5N-) dans le milieu interstellaire.Dans les environnements interstellaires où la densité d’électrons est relativement importante, le canal principal de formation de ces anions devrait être l’attachement électronique radiatif. Mais il manque aujourd’hui des données expérimentales et théoriques permettant d’évaluer cette hypothèse. D’autre part, le photodétachement est la principale cause de destruction de ces anions dans les nuages diffus et les régions de photodissociation. Une approche basée sur un développement monocentrique est appliquée à l’étude de ces deux processus opposés que sont le photodétachement et l’attachement électronique radiatif. Les résultats obtenus avec la présente méthode sont comparés à des données expérimentales et théoriques précédemment rapportées et montrent un bon accord. Cette méthode est ensuite utilisée pour déterminer les constantes de vitesse nécessaires pour confirmer si ces mécanismes sont cruciaux pour la chimie d’anions interstellaires. En plus des constantes de vitesse de formation et de destruction des anions, les constantes de vitesse d’excitation collisionnelle sont nécessaires pour modéliser les abondances observées des anions. Nous avons choisi de porter notre effort sur le calcul des constantes de vitesse de transition entre états rotationels de la molécule C3N- dans son état vibrationnel fondamental lors des collisions avec H2 et He en utilisant de nouvelles surfaces d’énergie potentielles. / The mechanisms of formation and destruction of molecular anions have become a field of special interest after the recent detection of six molecular anions (C4H-,C6H-, C8H-, CN-, C3N-, C5N-) in the interstellar medium. The main channel of formation of these anions is expected to be radiative electron attachment in environments where the density of electron is relatively important. There is however at themoment a lack of experimental and theoretical data allowing to assess this hypothesis. Photodetachment, on the other hand, is the main source of destruction of the anions in diffuse clouds and photodissociation regions. A single center expansion approach is applied to the study of both processes: photodetachment and radiative electron attachment. The results obtained with the present method are compared to previously reported experimental and theoretical data and show a good agreement.This method is then employed to determine the rate constants which are needed to confirm whether or not these mechanisms are crucial for the chemistry of the interstellar anions. Along with the formation and destruction rates, rotational excitation rate coefficients are needed to accurately model the observed anions abundances.We focus on the calculation of state-to-state rotational transitions rate coefficients of the C3N- molecule in its ground vibrational state in collisions with H2 and He using new potential energy surfaces