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We investigate the two- and three-body fragmentation of tribromomethane (bromoform, CHBr 3 ) resulting from multiple ionization by 28-femtosecond near-infrared laser pulses with a peak intensity of 6 × 10 14 W cm −2 . The analysis focuses on channels consisting exclusively of ionic fragments, which are measured by coincidence momentum imaging. The dominant two-body fragmentation channel is found to be Br + + CHBr 2 + . Weaker HBr + + CBr 2 + , CHBr + + Br 2 + , CHBr 2+ + Br 2 + , and Br + + CHBr 2 2+ channels, some of which require bond rearrangement prior to or during the fragmentation, are also observed. The dominant three-body fragmentation channel is found to be Br + + Br + + CHBr + . This channel includes both concerted and sequential fragmentation pathways, which we identify using the native frames analysis method. We compare the measured kinetic energy release and momentum correlations with the results of classical Coulomb explosion simulations and discuss the possible isomerization of CHBr 3 to BrCHBr–Br (iso-CHBr 3 ) prior to the fragmentation.more » « less
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The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1–11A1 (3sa1 ← 5b1) band and that predicted by Franck–Condon and Herzberg–Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0 eV.more » « less
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