Photoelectron-photoion-photoion coincidence (PEPIPICO) mass spectrometry is applied to Si 2p core ionization.The ion yield spectrum is compared to the spectrum of the tetramethylsilane molecule in order to point out resonances due to the Si-Si chemical bond. Simple coincidence mass spectra are dominated by the SiC3HgC fragment ion and do not show a strong dependence on photon wavelength. PEPIPICO spectra demonstrate that dissociation dynamics is dominated by stepwise fragmentation of SiC3H9+ and that double ionization always involves S i S i chemical bond rupture, shown to be faster than the Si-C rupture. We discuss the results in term of a fast decay of Si-Si into singly and doubly charged molecules followed by a cascade of slow fragmentation and isomerization of SiC3Hg+. IntroductionIn the past few years, considerable interest has been developed in the study of the dissociation processes of core excited moleculesId because of possible site-selective fragmentation pathways. Our recent work on tetrahedral silicon compound molecules such as SiH4,' Si(CH3)4,8 and SiF49 photoexcited near the Si 2p ionization edge shows that the nature of and the intensity ratio between single-and double-ionization decay channels vary strongly with the photon energy in the region of resonances, especially when the comparison is made below and above the core ionization limit, leading thus to different dissociation channels. For a discrete core-excited state, the excited electron in the valence electron cloud, which acts as a spectator or a nonspectator during the electronic decay channels, controls the nature of the final electronic states of the ion mostly with a single positive charge ion and its subsequent fragmentation. In contrast, in the core ionization continuum, normal Auger (including cascade Auger) processes explain the enhancement of double-(or triple-) ionization channels at the expense of single-ionization ones, giving rise to the observation of lighter fragments.Mass spectrometry of polymethylsilanes and siloxanes has been the subject of many studies because of the very high stability of the trimethylsilyl, Si(CH3)3+,In the present work, we report new mass spectrometry measurements with the multicoincidence technique known as PEPIPICO mass spectrometry or charge separation mass spectrometry)I3 (CSMS) applied to hexamethyldisilane, Si2(CH3)6 (HMDS), photoexcited near the Si 2p edge (i.e., from 100-to 130-eV photon energy). The interest of this molecule compared to the previously studied monosilane molecules is the presence of S i S i and Si-C bonds with different strengths. The different bonding pattern of the silicon atoms in HMDS is shown to affect the resonance pattern near the Si 2p edge compared to those of tetramethylsilane8 (Me&), for which the silicon atom is bound only to carbon atoms. The main purpose of the present work is to study the dissociation dynamics of such a core-excited molecule after single, double, and triple ionization, though this technique also allows analysis of metastable states. The problem of...

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Electronic state spectroscopy of limonene has been investigated using vacuum ultraviolet photoabsorption spectroscopy in the energy range 5.0-10.8 eV. The availability of a high resolution photon beam (~0.075 nm) enabled detailed analysis of the vibrational progressions and allowed us to propose, for the first time, new assignments for several Rydberg series. Excited states located in the 7.5-8.4 eV region have been studied for the first time. A He(I) photoelectron spectrum has also been recorded from 8.2 to 9.5 eV and compared to previous low resolution works. A new value of 8.521 ± 0.002 eV for the ground ionic state adiabatic ionisation energy is proposed. Absolute photoabsorption cross sections were derived in the 10-26 eV range from electron scattering data. All spectra presented in this paper represent the highest resolution data yet reported for limonene. These experiments are complemented by new ab initio calculations performed for the three most abundant conformational isomers of limonene, which we then used in the assignment of the spectral bands.

We present results on the valence level excitation, ionization and dissociation of adenine, using time-of-flight mass spectrometry and synchrotron radiation, in the vacuum ultraviolet (VUV) range of 12-21 eV. The measurements were performed using a gas-phase (Ne) harmonics filter in order to eliminate contributions from higher-order harmonics. Mass spectra were obtained using the photoelectron-photoion coincidence technique (PEPICO). The relative abundances for each ionic fragment and their mean kinetic energy release have been determined from the analysis of the corresponding peak shapes in the mass spectra. Comparison with the available photoelectron spectra and previous measurements allowed the assignment of the main features in the spectra. A discussion on the dissociative photoionization channels of this molecule has also been included. Due to our harmonics-free incident photon beam we were able to propose new appearance energy (AE) for the most important ionic channels in this energy range. The precursor ion, C(5)H(5)N(5)+, is the most abundant species (40% at 15 eV and 20% at 20 eV), which confirms the high stability of adenine upon absorption of VUV photons. We have observed other intense fragment ions such as: C(4)H(4)N(4)+, C(3)H(3)N(3) (+), C(2)H(2)N(2)+ and HCNH+. The production of the neutral HCN fragment represents up to 40% of the dissociative channels for this molecule as induced by VUV photons.

The dissociative photoionization of the chloroform and chloroform-d molecules has been studied in the valence region and around the chlorine 2p edge. Time-of-flight mass spectrometry in the coincidence mode-namely, photoelectron-photoion coincidence (PEPICO)-was employed. He I lamp and tunable synchrotron radiation were used as light sources. Total and partial ion yields have been recorded as a function of the photon energy. Singly, doubly, and triply ionized species have been observed below (195 eV), on (201 eV), and above (230 eV) the Cl 2p resonances. A definite degree of site-selective fragmentation was observed at the Cl 2p resonance as the relative contributions of several ionic species were seen to go through a maximum at 201 eV. At the same time all stable doubly charged ions were also observed at 198 eV (below the 2p resonances), resulting from direct ionization processes. Isotopic substitution is shown to provide a very efficient means of improving the mass resolution and assignment of unresolved peaks in spectra of CHCl(3), particularly for those fragments differing by a hydrogen atom. It is suggested that ultrafast fragmentation of the system following 2p excitation to a strongly antibonding state contributes to the large amount of Cl(+) observed in the PEPICO spectrum measured at 201 eV. Kinetic energy distributions were determined for the H(+), D(+), and Cl(+) fragments.

An experimental photochemistry study involving gas-and solid-phase amino acids (glycine, DL-valine, DL-proline) and nucleobases (adenine and uracil) under soft X-rays was performed.The aim was to test the molecular stabilities of essential biomolecules against ionizing photon fields inside dense molecular clouds and protostellar discs analogs. In these environments, the main energy sources are the cosmic rays and soft X-rays. The measurements were taken at the Brazilian Synchrotron Light Laboratory (LNLS), employing 150-eV photons. In situ sample analysis was performed by time-of-flight mass spectrometer (TOF-MS) and Fourier transform infrared (FTIR) spectrometer, for gas-and solid-phase analysis, respectively. The half-life of solid-phase amino acids, assumed to be present at grain mantles, is at least 3 × 10 5 and 3 × 10 8 yr inside dense molecular clouds and protoplanetary discs, respectively. We estimate that for gas-phase compounds these values increase 1 order of magnitude since the dissociation cross-section of glycine is lower in gas phase than in solid phase for the same photon energy. The half-life of solid-phase nucleobases is about 2-3 orders of magnitude longer than found for amino acids. The results indicate that nucleobases are much more resistant to ionizing radiation than amino acids. We consider these implications for the survival and transfer of biomolecules in space environments.

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Partial ion yields from photoionization of SiF4 have been measured with time-of-flight mass spectrometry, photoion–photoion coincidence and triple photoion coincidence techniques using synchrotron radiation from 100 to 136 eV, in the region of the silicon 2p edge where strong resonances are found. From the photon energy dependence of positive ion pairs and of doubly charged fragment intensities, with a suitable normalization procedure, we have estimated the total double photoionization cross section. Below the Si2p edge, the double to single dissociative ionization branching ratio follows the resonance behavior, and is consistent with the photoelectron results of de Souza et al. (Paper I) and discussed in terms of multibond breaking dissociation pathways of residual excited ions (singly and doubly charged) produced by resonant Auger decay processes. Above the Si2p edge, the fragmentation is found to originate from dissociative double ionization occurring after normal Auger processes. The small additional contribution of triple dissociative ionization is consistent with a second order Auger process. In contrast, the underlying valence ionization continuum is responsible for all parent intensity and most of the SiF+3 fragment expected from the normal dissociative ionization channels. The measurement of appearance energies of fragment ion pairs by the photoion–photoion coincidence method, offers a direct measurement of the first direct double ionization onset in SiF4 and new values for other dissociative SiF2+4 states which complement those found by Auger spectroscopy.