Non-radiative processes in protonated diazines, pyrimidine bases and an aromatic azine

International audienceThe excited state lifetimes of DNA bases are often very short due to very efficient non-radiative processes assigned to the pp*–np* coupling. A set of protonated aromatic diazine molecules (pyridazine, pyrimidine and pyrazine C4H5N2+) and protonated pyrimidine DNA bases (cytosine, uracil and thymine), as well as the protonated pyridine (C5H6N+), have been investigated. For all these molecules except one tautomer of protonated uracil (enol–keto), electronic spectroscopy exhibits vibrational line broadening. Excited state geometry optimization at the CC2 level has been conducted to find out whether the excited state lifetimes measured from line broadening can be correlated to the calculated ordering of the pp* and np* states and the pp*–np* energy gap. The short lifetimes, observed when one nitrogen atom of the ring is not protonated, can be rationalized by relaxation of the pp* state to the np* state or directly to the electronic ground state through ring puckering

Molécules et nanoparticules aromatiques du milieu interstellaire : production et caractérisation au laboratoire

The work presented in this thesis deals with laboratory astrophysics experiments of aromatic compounds, mostly studied in conditions similar to those encountered in interstellar and circumstellar environments, including cosmic rays and UV irradiations. These are the source of mid-infrared emission bands whose carriers are supposed to be composed mainly of Polycyclic Aromatic Hydrocarbons (PAHs) and aromatic nanoparticles.A new spectrometer, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), containing a replica of the circular variable filters of the ISOCAM instrument on-board the ISO satellite, was developed and characterized in this thesis. This instrument was used to measure the infrared de-excitation in the CH stretching mode region (3.3 µm or 3000 cm-1) from benzene derivatives and from naphthalene at room temperature, following the absorption of a single UV photon. With the support of modelling, IR emission spectroscopy is a powerful tool for understanding the effects of anharmonicity related to the internal energy, isomerization and also the non-adiabatic intramolecular dynamics through the new technique of IR fluorescence excitation spectroscopy. This work is preliminary to the infrared fluorescence measurement of low-temperature gas phase aromatic nanoparticles produced by a low pressure flame, in order to compare the laboratory spectra with astrophysical observations.Cosmic-ray energy deposition has been studied with another experiment: the ionic irradiation of interstellar and circumstellar dust analogues (soot produced by the low pressure flame) highlights a chemical reorganization. Soot is characterized by complementary diagnostics such as High Resolution Transmission Electron Microscopy, Fourier Transform Infrared spectroscopy and Raman spectroscopy. The results help identify the analogue nanostructures and better identify the astrophysical spectral signatures (interpretation of the 7.7 µm band as a defect band). Through these experiences, we hope to improve our understanding of the structure, growth and evolution of the dust, in the astrophysical context.Ce travail de thèse traite d'expériences d'astrophysique de laboratoire sur des matériaux aromatiques, étudiés pour la plupart dans des conditions proches de celles rencontrées dans les milieux interstellaire et circumstellaire, comprenant rayons cosmiques et irradiations UV. Ces dernières sont à l’origine de bandes d'émission dans l'infrarouge moyen, dont les porteurs supposés sont principalement les Hydrocarbures Aromatiques Polycycliques (PAHs) et les nanoparticules aromatiques. Un nouveau spectromètre, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), contenant une réplique des filtres circulaires variables à bord de l'instrument ISOCAM du satellite ISO, a été mis au point et caractérisé au cours de cette thèse. Cet instrument a permis de mesurer la désexcitation infrarouge dans la région des modes d'élongations CH (3.3 µm, soit 3000 cm-1) des dérivés du benzène et du naphtalène à température ambiante, suite à l’absorption d'un photon UV. Ceci montre, avec l’appui de la modélisation, que la spectroscopie d’émission IR est un outil puissant permettant de comprendre les effets d'anharmonicité liés à l'énergie interne, l’isomérisation voire même la dynamique intramoléculaire non-adiabatique, au travers de la spectroscopie d'excitation de fluorescence infrarouge (une nouvelle technique). Ce travail est préliminaire à la future mesure de fluorescence infrarouge de nanoparticules aromatiques en phase gazeuse et à basse température produites par une flamme basse pression, dans le but de comparer les spectres de laboratoire avec les observations astrophysiques. Le dépôt d'énergie par les rayons cosmiques a été étudié grâce à une autre expérience, l'irradiation ionique d'analogues de poussières interstellaires et circumstellaires (suies produites par la flamme basse pression), mettant en évidence une réorganisation chimique. Les suies sont caractérisées par différents diagnostics complémentaires tels que la Microscopie Electronique en Transmission à Haute Résolution et les spectroscopies infrarouge à Transformée de Fourier et Raman. L'ensemble des informations tirées permet de mieux cerner la nanostructuration des analogues et ainsi mieux identifier les différentes signatures spectrales astrophysiques (interprétation de la bande à 7.7 µm comme une bande de défauts). Grâce à ces expériences, nous espérons améliorer notre compréhension de la structure, croissance et évolution de la poussière, d'un point de vue astrophysique

Aromatic molecules and nanoparticles in the interstellar medium : production and characterization in the laboratory

Ce travail de thèse traite d'expériences d'astrophysique de laboratoire sur des matériaux aromatiques, étudiés pour la plupart dans des conditions proches de celles rencontrées dans les milieux interstellaire et circumstellaire, comprenant rayons cosmiques et irradiations UV. Ces dernières sont à l’origine de bandes d'émission dans l'infrarouge moyen, dont les porteurs supposés sont principalement les Hydrocarbures Aromatiques Polycycliques (PAHs) et les nanoparticules aromatiques. Un nouveau spectromètre, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), contenant une réplique des filtres circulaires variables à bord de l'instrument ISOCAM du satellite ISO, a été mis au point et caractérisé au cours de cette thèse. Cet instrument a permis de mesurer la désexcitation infrarouge dans la région des modes d'élongations CH (3.3 µm, soit 3000 cm-1) des dérivés du benzène et du naphtalène à température ambiante, suite à l’absorption d'un photon UV. Ceci montre, avec l’appui de la modélisation, que la spectroscopie d’émission IR est un outil puissant permettant de comprendre les effets d'anharmonicité liés à l'énergie interne, l’isomérisation voire même la dynamique intramoléculaire non-adiabatique, au travers de la spectroscopie d'excitation de fluorescence infrarouge (une nouvelle technique). Ce travail est préliminaire à la future mesure de fluorescence infrarouge de nanoparticules aromatiques en phase gazeuse et à basse température produites par une flamme basse pression, dans le but de comparer les spectres de laboratoire avec les observations astrophysiques. Le dépôt d'énergie par les rayons cosmiques a été étudié grâce à une autre expérience, l'irradiation ionique d'analogues de poussières interstellaires et circumstellaires (suies produites par la flamme basse pression), mettant en évidence une réorganisation chimique. Les suies sont caractérisées par différents diagnostics complémentaires tels que la Microscopie Electronique en Transmission à Haute Résolution et les spectroscopies infrarouge à Transformée de Fourier et Raman. L'ensemble des informations tirées permet de mieux cerner la nanostructuration des analogues et ainsi mieux identifier les différentes signatures spectrales astrophysiques (interprétation de la bande à 7.7 µm comme une bande de défauts). Grâce à ces expériences, nous espérons améliorer notre compréhension de la structure, croissance et évolution de la poussière, d'un point de vue astrophysique.The work presented in this thesis deals with laboratory astrophysics experiments of aromatic compounds, mostly studied in conditions similar to those encountered in interstellar and circumstellar environments, including cosmic rays and UV irradiations. These are the source of mid-infrared emission bands whose carriers are supposed to be composed mainly of Polycyclic Aromatic Hydrocarbons (PAHs) and aromatic nanoparticles.A new spectrometer, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), containing a replica of the circular variable filters of the ISOCAM instrument on-board the ISO satellite, was developed and characterized in this thesis. This instrument was used to measure the infrared de-excitation in the CH stretching mode region (3.3 µm or 3000 cm-1) from benzene derivatives and from naphthalene at room temperature, following the absorption of a single UV photon. With the support of modelling, IR emission spectroscopy is a powerful tool for understanding the effects of anharmonicity related to the internal energy, isomerization and also the non-adiabatic intramolecular dynamics through the new technique of IR fluorescence excitation spectroscopy. This work is preliminary to the infrared fluorescence measurement of low-temperature gas phase aromatic nanoparticles produced by a low pressure flame, in order to compare the laboratory spectra with astrophysical observations.Cosmic-ray energy deposition has been studied with another experiment: the ionic irradiation of interstellar and circumstellar dust analogues (soot produced by the low pressure flame) highlights a chemical reorganization. Soot is characterized by complementary diagnostics such as High Resolution Transmission Electron Microscopy, Fourier Transform Infrared spectroscopy and Raman spectroscopy. The results help identify the analogue nanostructures and better identify the astrophysical spectral signatures (interpretation of the 7.7 µm band as a defect band). Through these experiences, we hope to improve our understanding of the structure, growth and evolution of the dust, in the astrophysical context

Molécules et nanoparticules aromatiques du milieu interstellaire (production et caractérisation au laboratoire)

Ce travail de thèse traite d'expériences d'astrophysique de laboratoire sur des matériaux aromatiques, étudiés pour la plupart dans des conditions proches de celles rencontrées dans les milieux interstellaire et circumstellaire, comprenant rayons cosmiques et irradiations UV. Ces dernières sont à l origine de bandes d'émission dans l'infrarouge moyen, dont les porteurs supposés sont principalement les Hydrocarbures Aromatiques Polycycliques (PAHs) et les nanoparticules aromatiques. Un nouveau spectromètre, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), contenant une réplique des filtres circulaires variables à bord de l'instrument ISOCAM du satellite ISO, a été mis au point et caractérisé au cours de cette thèse. Cet instrument a permis de mesurer la désexcitation infrarouge dans la région des modes d'élongations CH (3.3 m, soit 3000 cm-1) des dérivés du benzène et du naphtalène à température ambiante, suite à l absorption d'un photon UV. Ceci montre, avec l appui de la modélisation, que la spectroscopie d émission IR est un outil puissant permettant de comprendre les effets d'anharmonicité liés à l'énergie interne, l isomérisation voire même la dynamique intramoléculaire non-adiabatique, au travers de la spectroscopie d'excitation de fluorescence infrarouge (une nouvelle technique). Ce travail est préliminaire à la future mesure de fluorescence infrarouge de nanoparticules aromatiques en phase gazeuse et à basse température produites par une flamme basse pression, dans le but de comparer les spectres de laboratoire avec les observations astrophysiques. Le dépôt d'énergie par les rayons cosmiques a été étudié grâce à une autre expérience, l'irradiation ionique d'analogues de poussières interstellaires et circumstellaires (suies produites par la flamme basse pression), mettant en évidence une réorganisation chimique. Les suies sont caractérisées par différents diagnostics complémentaires tels que la Microscopie Electronique en Transmission à Haute Résolution et les spectroscopies infrarouge à Transformée de Fourier et Raman. L'ensemble des informations tirées permet de mieux cerner la nanostructuration des analogues et ainsi mieux identifier les différentes signatures spectrales astrophysiques (interprétation de la bande à 7.7 m comme une bande de défauts). Grâce à ces expériences, nous espérons améliorer notre compréhension de la structure, croissance et évolution de la poussière, d'un point de vue astrophysique.The work presented in this thesis deals with laboratory astrophysics experiments of aromatic compounds, mostly studied in conditions similar to those encountered in interstellar and circumstellar environments, including cosmic rays and UV irradiations. These are the source of mid-infrared emission bands whose carriers are supposed to be composed mainly of Polycyclic Aromatic Hydrocarbons (PAHs) and aromatic nanoparticles.A new spectrometer, FIREFLY (Fluorescence in the InfraRed from Excited FLYing molecules), containing a replica of the circular variable filters of the ISOCAM instrument on-board the ISO satellite, was developed and characterized in this thesis. This instrument was used to measure the infrared de-excitation in the CH stretching mode region (3.3 m or 3000 cm-1) from benzene derivatives and from naphthalene at room temperature, following the absorption of a single UV photon. With the support of modelling, IR emission spectroscopy is a powerful tool for understanding the effects of anharmonicity related to the internal energy, isomerization and also the non-adiabatic intramolecular dynamics through the new technique of IR fluorescence excitation spectroscopy. This work is preliminary to the infrared fluorescence measurement of low-temperature gas phase aromatic nanoparticles produced by a low pressure flame, in order to compare the laboratory spectra with astrophysical observations.Cosmic-ray energy deposition has been studied with another experiment: the ionic irradiation of interstellar and circumstellar dust analogues (soot produced by the low pressure flame) highlights a chemical reorganization. Soot is characterized by complementary diagnostics such as High Resolution Transmission Electron Microscopy, Fourier Transform Infrared spectroscopy and Raman spectroscopy. The results help identify the analogue nanostructures and better identify the astrophysical spectral signatures (interpretation of the 7.7 m band as a defect band). Through these experiences, we hope to improve our understanding of the structure, growth and evolution of the dust, in the astrophysical context.PARIS11-SCD-Bib. électronique (914719901) / SudocSudocFranceF

Photodissociation Electronic Spectra of Cold Protonated Quinoline and Isoquinoline in the Gas Phase

International audiencePhotofragmentation electronic spectra of isolated single-isomeric N-protonated quinoline (quinolinium) and isoquinoline (isoquinolinium) ions have been measured at a temperature of ∼40 K using a mass-selective, 10 cm–1 spectral resolution, photodissociation spectrometer. Additionally, ab initio adiabatic transition energies calculated using the RI-ADC(2) method have been employed to assist in the assignment of the spectra. Three electronic transitions having ππ* character were clearly evidenced for both protonated ions within the UV and deep-UV spectral ranges. The corresponding spectra at room temperature were previously reported by Hansen et al., together with TD-DFT calculations and a careful analysis of the possible fragmentation mechanisms. This information will be complemented in the present study by appending better resolved spectra, characteristic of cold ions, in which well-defined vibrational progressions associated with the S1 ← S0 and S3 ← S0 transitions exhibit clear 0–0 bands at hν0–0 = 27868 and 42230 cm–1, for protonated quinoline, and at hν0–0 = 28043 and 41988 cm–1, for protonated isoquinoline. Active vibrations in the spectra were assigned with the help of calculated normal modes, looking very similar to those of the structurally related protonated naphthalene. Finally, we have observed that the bandwidths associated with the deep-UV S3 ← S0 transition denote a lifetime for the S3 excited state in the subpicosecond time scale, in contrast with that of S1

Photodissociation Electronic Spectra of Cold Protonated Quinoline and Isoquinoline in the Gas Phase

International audiencePhotofragmentation electronic spectra of isolated single-isomeric N-protonated quinoline (quinolinium) and isoquinoline (isoquinolinium) ions have been measured at a temperature of ∼40 K using a mass-selective, 10 cm–1 spectral resolution, photodissociation spectrometer. Additionally, ab initio adiabatic transition energies calculated using the RI-ADC(2) method have been employed to assist in the assignment of the spectra. Three electronic transitions having ππ* character were clearly evidenced for both protonated ions within the UV and deep-UV spectral ranges. The corresponding spectra at room temperature were previously reported by Hansen et al., together with TD-DFT calculations and a careful analysis of the possible fragmentation mechanisms. This information will be complemented in the present study by appending better resolved spectra, characteristic of cold ions, in which well-defined vibrational progressions associated with the S1 ← S0 and S3 ← S0 transitions exhibit clear 0–0 bands at hν0–0 = 27868 and 42230 cm–1, for protonated quinoline, and at hν0–0 = 28043 and 41988 cm–1, for protonated isoquinoline. Active vibrations in the spectra were assigned with the help of calculated normal modes, looking very similar to those of the structurally related protonated naphthalene. Finally, we have observed that the bandwidths associated with the deep-UV S3 ← S0 transition denote a lifetime for the S3 excited state in the subpicosecond time scale, in contrast with that of S1

Quantifying non-thermal desorption from molecular ices - Comparative study of photon and electron irradiation in the valence- and core-shell energy ranges

International audienc

Quantifying non-thermal desorption from molecular ices - Comparative study of photon and electron irradiation in the valence- and core-shell energy ranges

International audienc

Development of Ultraviolet-Ultraviolet Hole-Burning Spectroscopy for Cold Gas-Phase Ions

International audienceA new ultraviolet-ultraviolet hole-burning (UV-UV HB) spectroscopic scheme has been developed for cold gas-phase ions in a quadrupole ion trap (QIT) connected with a time-of-flight (TOF) mass spectrometer. In this method, a pump UV laser generates a population hole for the ions trapped in the cold QIT, and a second UV laser (probe) monitors the population hole for the ions extracted to the field-free region of the TOF mass spectrometer. Here, the neutral fragments generated by the UV dissociation of the ions with the second laser are detected. This UV-UV HB spectroscopy was applied to protonated dibenzylamine and to protonated uracil. Protonated uracil exhibits two strong electronic transitions; one has a band origin at 31760 cm-1 and the other at 39000 cm-1. From the UV-UV HB measurement and quantum chemical calculations, the lower-energy transition is assigned to the enol-keto tautomer and the higher-energy one to the enol-enol tautomer