Branching ratios in the dissociative photoionization of iodomethane by photoelectron photoion coincidence.

Iodomethane yields ten fragment ions after valence photoionization, in part by multiple dissociation pathways for each, thanks to a plethora of electronic states available in the parent ion as well as in the fragments. The comprehensive breakdown diagram from 11 eV to the double ionization onset, i.e., 26.7 eV, is recorded at high resolution using double imaging photoelectron photoion coincidence spectroscopy with synchrotron vacuum ultraviolet radiation. Based on fragment ion groupings, the changing branching ratios between these groups and between fragment ions within each group, as well as ancillary thermochemistry, we provide an overview of the dissociation pathways at play. Statistical and impulsive dissociations are identified using kinetic energy release analysis. Finally, a newly observed regime change is discussed in double ionization, whereby coincident H+ + I+ formation dominates over a 4 eV photon energy range, outcompeting the normally prevailing CH3+ + I+ channel.

High energy Rydberg and ion-pair states, state mixing and excitation dynamics of HI.

Mass resolved multiphoton ionization data for two-photon resonant excitations (REMPI) in the region of 74 000-75 000 cm-1 were recorded for HI. Spectra structures of fragment and molecular ions derived from the data were analyzed to derive information relevant to the energetics and state mixing of ion-pair and Rydberg resonance states as well as for the excitation dynamics. Four new ion-pair vibrational states (V1Σ+(v' = m + i); i = 16-19) and two Rydberg states (j3Σ-(0+; v' = 1) and N1Π1(v' = 2)) were identified and characterized. Spectral perturbations allowed characterization and quantization of both homogeneous and heterogeneous state interactions and mixing of the Rydberg states and ion-pair states. Intensity alterations, with respect to energy level excitations and ion masses, are found to be clear indications of state mixing as well as branching into different fragmentation (both photodissociation and photoionization) channels.

Two-color studies of CH3Br excitation dynamics with MPI and slice imaging.

Two-color pump-probe experiments were performed to explore the multiphoton dynamics of CH3Br at high excitation energies of 8-10 eV, involving two-photon resonant excitations to a number of np and nd Rydberg states (pump) followed by REMPI detection (probe) of the Br, Br* and CH3(X) photoproducts. Slice images of Br+ and CH3+ ions were recorded in pump-only, probe-only and pump and probe experiments. Kinetic-energy release spectra (KERs), as well as spatial anisotropy parameters, were extracted from the images to identify the processes and the dynamics involved. Predissociation channels, following the two-photon resonant excitations and non-resonant photodissociation forming CH3(X) and Br/Br*, were identified and characterized. Furthermore, the probe excitations for CH3(X) involved near-resonant excitations to lower energy 5s Rydberg states of CH3Br. In three-photon excitation processes, a striking contrast is seen between excitations via the p/d and the s Rydberg states. Involvement of high-energy interactions between Rydberg and ion-pair states is identified.

Multiphoton Rydberg and valence dynamics of CH3Br probed by mass spectrometry and slice imaging.

The multiphoton dynamics of CH3Br were probed by Mass Resolved MultiPhoton Ionization (MR-MPI), Slice Imaging and Photoelectron Imaging in the two-photon excitation region of 66 000 to 80 000 cm-1. Slice images of the CH3+ and Br+ photoproducts of ten two-photon resonant transitions to np and nd Rydberg states of the parent molecule were recorded. CH3+ ions dominate the mass spectra. Kinetic energy release spectra (KERs) were derived from slice and photoelectron images and anisotropy parameters were extracted from the angular distributions of the ions to identify the processes and the dynamics involved. At all wavelengths we observe three-photon excitations, via the two-photon resonant transitions to molecular Rydberg states, forming metastable, superexcited (CH3Br#) states which dissociate to form CH3 Rydberg states (CH3**) along with Br/Br*. A correlation between the parent Rydberg states excited and CH3** formed is evident. For the three highest excitation energies used, the CH3Br# metastable states also generate high kinetic energy fragments of CH3(X) and Br/Br*. In addition for two out of these three wavelengths we also measure one-photon photolysis of CH3Br in the A band forming CH3(X) in various vibrational modes and bromine atoms in the ground (Br) and spin-orbit excited (Br*) states.

Long term puzzles of the CH and CD energetics and related phenomena revisited; solutions sought through REMPI-photofragmentations of bromomethanes.

Ever since the pioneering work by Herzberg and Johns in 1969 (The Astrophysical Journal, 1969, 158, 399) the spectral assignment and the energetics of the fundamental molecular fragment CH, in the region of 63 000-65 000 cm(-1) (7.81-8.06 eV), have remained a puzzle to a large extent. The dissociation of bromoform and deuterated bromoform following two-photon resonance excitations to molecular Rydberg states forms the fragment species CH* and CD* in the excited state A(2)Δ(v' =0) as well as carbon and bromine atoms in the ground and first excited states, C/C* and Br/Br*. Further (1r + 1i)REMPI of CH* and CD* resonance excites the fragments to the energy region of concern, whereas the atom fragments were identified by further (2r + 1i)REMPI. Analysis based on spectral simulations, isotope shifts and comparison with other data allowed spectral identifications, assignments and partial characterization of four highly excited bound states for each of the molecular fragments (CH**/CD**); including the (3)(2)Π valence state and the (4)(2)Π Rydberg state, for the first time. Perturbations, shown as line-shifts, line-intensity and/or line-width alterations, due to the level-to-level state interactions between the bound states and predissociations by a repulsive state are recognized. Recording of C(+) signals in REMPI of several bromomethanes for a one-photon energy of about 40 333 cm(-1) allows the clarification of a mystery concerning a broad C(+) band frequently observed. This work, presented, demonstrates the usefulness of molecular REMPI for fragment analysis.

Effect of a triplet to singlet state interaction on photofragmentation dynamics: highly excited states of HBr probed by VMI and REMPI as a case study.

Analysis of mass resolved spectra as well as velocity map images derived from resonance enhanced multiphoton ionization (REMPI) of HBr via resonance excitations to mixed Rydberg (6pπ 3Σ-(v' = 0)) and valence (ion-pair) (V 1Σ+(v' = m + 17)) states allows characterization of the effect of a triplet-to-singlet state interaction on further photoexcitation and photoionization processes. The analysis makes use of rotational spectra line shifts, line intensity alterations, kinetic energy release spectra as well as angular distributions. Energy-level-dependent state mixing of the resonance excited states is quantified and photoexcitation processes, leading to H+ formation, are characterized in terms of the states and fragmentation processes involved, depending on the state mixing.