This thesis presents experimental studies of gas phasemolecular relaxation after excitation with synchrotron photonsin the 15-35 eV and in the 70-350 eV regions. In the 15-35 eV region, molecular relaxation by neutraldissociation processes and non Franck-Condon effects in N2 and O2 molecules have beenstudied by means of dispersed fluorescence and photoelectronspectroscopy experimental techniques, respectively. From thedispersed fluorescence data, excitation functions for themeasured atomic fluorescence spectra have been obtained. Fromthe recorded photoelectron spectra vibrational branching ratioshave been produced. The results obtained reveal that Rydbergseries and singly and doubly excited valence states of theappropriate symmetry energetically accessible in the studiedregion and interactions between themaccount for most of theobserved effects in these two type of experiments. In the 70-350 eV range, molecular relaxation processesresulting in fragmentation of CD4 and SF6 after absorption ofsynchrotron light have been studied by energy resolved electronion coincidence technique using a multicoincidence experimentalstation developed by our group during the last five years forsuch type of experiments. The coincidence measurements yieldedmass spectra from which information about the kinematics of thedetected fragments has been deduced by means of Monte Carlosimulations of the experimental peak shapes. The obtainedresults show completely different dissociation patternsdepending on the molecular electronic states studied. Thesepatterns reflect the bonding properties of the excited orbitalsand they permit the description and in some cases theidentification of the different molecular relaxation pathwaysobserved. The achievements presented in this thesis exemplifythe potential of the multicoincidence station used in thereported experiments.

<p>This thesis presents experimental studies of gas phasemolecular relaxation after excitation with synchrotron photonsin the 15-35 eV and in the 70-350 eV regions.</p><p>In the 15-35 eV region, molecular relaxation by neutraldissociation processes and non</p><p>Franck-Condon effects in N2 and O2 molecules have beenstudied by means of dispersed fluorescence and photoelectronspectroscopy experimental techniques, respectively. From thedispersed fluorescence data, excitation functions for themeasured atomic fluorescence spectra have been obtained. Fromthe recorded photoelectron spectra vibrational branching ratioshave been produced. The results obtained reveal that Rydbergseries and singly and doubly excited valence states of theappropriate symmetry energetically accessible in the studiedregion and interactions between themaccount for most of theobserved effects in these two type of experiments.</p><p>In the 70-350 eV range, molecular relaxation processesresulting in fragmentation of CD4 and SF6 after absorption ofsynchrotron light have been studied by energy resolved electronion coincidence technique using a multicoincidence experimentalstation developed by our group during the last five years forsuch type of experiments. The coincidence measurements yieldedmass spectra from which information about the kinematics of thedetected fragments has been deduced by means of Monte Carlosimulations of the experimental peak shapes. The obtainedresults show completely different dissociation patternsdepending on the molecular electronic states studied. Thesepatterns reflect the bonding properties of the excited orbitalsand they permit the description and in some cases theidentification of the different molecular relaxation pathwaysobserved. The achievements presented in this thesis exemplifythe potential of the multicoincidence station used in thereported experiments.</p>

Abstract Experimental synchrotron radiation induced electron- and ion spectroscopies together with electron-ion and ion-ion coincidence techniques as well as electron energy loss spectroscopy have been used to study the electronic properties of several vapor phase samples. In this thesis studies of the electronic structure and fragmentation of Sb4 clusters, photo- and Auger electron spectroscopy of atomic Si and Pb as well as ultra high resolution VUV absorption of vapor phase KF molecules have been performed. The instrumentation and techniques used in the studies, especially the electron energy loss apparatus and the newly built ultra high resolution FINEST beamline branch, are presented.

In this thesis, multiple ionisation processes of free atoms and molecules upon single photon absorption are studied by means of a versatile multi-electron-ion coincidence spectroscopy method based on a magnetic bottle, primarily in combination with synchrotron radiation. The latter offered the possibility to access not only valence but also core levels, revealing processes, which promote the target systems into different charge states. One study focuses on double and triple ionisation processes of acetaldehyde (ethanal) in the valence region as well as single and double Auger decay of initial 1s core vacancies. The latter are investigated site-selectively for the two chemically different carbon atoms of acetaldehyde, scrutinising theoretical predictions specifically made for that system. A related study concentrates on core-valence double ionisation spectra of acetaldehyde, which have been investigated in the light of a previously established empirical model, and which have been used as test cases for analysing this kind of spectra by means of quantum chemical electronic structure methods of increasing sophistication. A third study investigates site-specific fragmentation upon 1s photoionisation of acetaldehyde using a magnetic bottle augmented with an in-line ion time-of-flight mass spectrometer. Experimental evidence is presented that bond rupture occurs with highest probability in the vicinity of the initial charge localisation and possible mechanisms are discussed. A site-specificity parameter P∆ is introduced to show that differences in fragmentation behavior between initial ionisations at chemically different carbon atoms probably persist even for identical internal energy contents in the nascent dications. In another study where both electrons and ions from Auger decay of core-excited and core-ionised states of CO2 are detected in coincidence, it is confirmed that O2+ is formed specifically in Auger decay from the C1s → π* and O1s → π* resonances, suggesting a decisive role of the π* orbital in the molecular rearrangement. Also, the molecular rearrangement is found to occur by bending in the resonant states, and O2+ is produced by both single and double Auger decay. A new version of the multi-electron-ion coincidence method, where the ion time-of-flight spectrometer is mounted perpendicularly to the electron flight tube, which affects less the electron resolution and which allows for position sensitive detection of the ions, is employed in combination with tunable soft X-rays to reveal the branching ratios to final Xen+ states with 2 &lt; n &lt; 9 from pure 4d-1, 4p-1, 4s-1, 3d-1 and 3p-1 Xe+ hole states. The coincident electron spectra give information on the Auger cascade pathways. / <p>Byte av lokal vid disputation till Polhemssalen.</p>

Cette thèse est dédiée à l’étude et l’exploitation des propriétés remarquables de la distribution angulaire des photoélectrons dans le référentiel moléculaire (MFPAD pour Molecular Frame Photoelectron Angular Distribution). Cette observable sensible permet de caractériser au meilleur niveau à la fois les processus de photoionisation (PI) de petites molécules, par la détermination des modules et phases relatives des éléments de matrice dipolaire, et l’état de polarisation du rayonnement ionisant, entièrement encodé dans son expression sous la forme des paramètres de Stokes (s1, s2, s3), qui constituent les deux axes du travail présenté. La mesure des MFPADs combine une technique de spectroscopie tridimensionnelle en coïncidence des vecteurs vitesse du photoélectron et du photoion issus de la même réaction de photoionisation dissociative (PID) à l’utilisation de différentes sources de lumière : le rayonnement synchrotron d’une part, sur les lignes DESIRS et PLEIADES (SOLEIL), et le rayonnement harmonique (HHG) généré par l’interaction d’un champ laser intense sur une cible gazeuse d’autre part, sur la plateforme PLFA (SLIC, groupe Attophysique du LIDyL, CEA Saclay).La première partie de la thèse est consacrée à la caractérisation complète de l’état de polarisation d’un rayonnement incident. Pour cela, une méthode originale de « polarimétrie moléculaire » est introduite et qualifiée sur la ligne DESIRS équipée d’un polarimètre optique VUV étalon. Mise en œuvre pour déterminer complètement l’ellipse de polarisation du rayonnement HHG produit dans différentes configurations sur la source secondaire XUV PLFA, elle conduit à des résultats originaux incluant notamment la distinction entre les composantes circulaire et non polarisée du rayonnement étudié.La seconde partie porte sur la PID des molécules H2, D2 et HD induite à résonance avec les états doublement excités Q1 et Q2 par une lumière polarisée circulairement. Dans cette région énergétique (30-35 eV) où l’ionisation directe, l’autoionisation et la dissociation sont en compétition sur une échelle de quelques femtosecondes, l’excitation photonique donne lieu à une dynamique couplée électron-noyau ultrarapide. Les asymétries remarquables observées dans le dichroïsme circulaire dans le référentiel moléculaire, comparées aux calculs quantiques du groupe de F. Martín (UAM, Madrid), constituent une sonde sensible des interférences quantiques entre des chemins réactionnels indiscernables impliquant des cœurs ioniques de symétrie u/g différente. / This is thesis is dedicated to the study and the use of the remarkable properties of the molecular frame photoelectron angular distribution (MFPAD). This observable is a very sensitive probe of both the photoionization (PI) processes in small molecules, through the determination of the magnitudes and relative phases of the dipole matrix elements, and the polarization state of the ionizing light, which is entirely encoded in the MFPAD in terms of the Stokes parameters (s1, s2, s3). MFPAD measurements take advantage of dissociative photoionization (DPI) processes by combining an electron-ion 3D momentum spectroscopy technique with the use of different radiation facilities: SOLEIL synchrotron (DESIRS and PLEIADES beamlines) and the XUV PLFA beamline (SLIC, LIDyL Attophysics group, CEA Saclay) based on the interaction of a strong laser field with a gaseous target called high harmonic generation (HHG).The first part of the thesis is devoted to the complete characterization of the polarization state of an incoming radiation. In this context, an original “molecular polarimetry” method is introduced and demonstrated by comparison with a VUV optical polarimeter available on the DESIRS beamline. Using this method to determine the full polarization ellipse of HHG radiation generated in different conditions on the XUV PLFA facility leads to original results that include the challenging disentanglement of the circular and unpolarized components of the studied radiation.The second part deals with the study of DPI of the H2, D2 and HD molecules induced by circularly polarized light at resonance with the doubly excited states Q1 and Q2. In this energy region (30-35 eV) where direct ionization, autoionization and dissociation compete on a femtosecond timescale, the photonic excitation gives rise to complex ultrafast electronic and nuclear coupled dynamics. The remarkable asymmetries observed in the circular dichroism in the molecular frame, compared to quantum calculations of the group of F. Martín (UAM, Madrid), constitute a very sensitive probe of the quantum interferences between indistinguishable DPI channels involving ionic states of different u/g symmetry.