High-repetition-rate and high-photon-flux 70 eV high-harmonic source for coincidence ion imaging of gas-phase molecules

Unraveling and controlling chemical dynamics requires techniques to image structural changes of molecules with femtosecond temporal and picometer spatial resolution. Ultrashort-pulse x-ray free-electron lasers have significantly advanced the field by enabling advanced pump-probe schemes. There is an increasing interest in using table-top photon sources enabled by high-harmonic generation of ultrashort-pulse lasers for such studies. We present a novel high-harmonic source driven by a 100 kHz fiber laser system, which delivers 10$^{11}$ photons/s in a single 1.3 eV bandwidth harmonic at 68.6 eV. The combination of record-high photon flux and high repetition rate paves the way for time-resolved studies of the dissociation dynamics of inner-shell ionized molecules in a coincidence detection scheme. First coincidence measurements on CH$_3$I are shown and it is outlined how the anticipated advancement of fiber laser technology and improved sample delivery will, in the next step, allow pump-probe studies of ultrafast molecular dynamics with table-top XUV-photon sources. These table-top sources can provide significantly higher repetition rates than the currently operating free-electron lasers and they offer very high temporal resolution due to the intrinsically small timing jitter between pump and probe pulses

Isomer-dependent fragmentation dynamics of inner-shell photoionized difluoroiodobenzene

The fragmentation dynamics of 2,6- and 3,5-difluoroiodobenzene after iodine 4d inner-shell photoionization with soft X-rays are studied using coincident electron and ion momentum imaging. By analyzing the momentum correlation between iodine and fluorine cations in three-fold ion coincidence events, we can distinguish the two isomers experimentally. Classical Coulomb explosion simulations are in overall agreement with the experimentally determined fragment ion kinetic energies and momentum correlations and point toward different fragmentation mechanisms and time scales. While most three-body fragmentation channels show clear evidence for sequential fragmentation on a time scale larger than the rotational period of the fragments, the breakup into iodine and fluorine cations and a third charged co-fragment appears to occur within several hundred femtoseconds

Intensity-dependent near-threshold ionization of Kr in the vacuum-uv

In this work, we present measurements of the intensity-dependent photoelectron spectrum of Kr irradiated by the FLASH FEL tuned to a photon energy of 25.8 eV. Intensity dependent photoelectron spectra were obtained with the aid of a Velocity Map Imaging (VMI) spectrometer. As the FEL photon energy is close to threshold, two photon sequential double ionization is favoured. The number of open channels is kept to a minimum and leading to a simple description of the process

Reactivity of Aromatic Radical Cations. Rate Constants for Reactions of 9-Phenyl- and 9,10-Diphenylanthracene Radical Cations with Acyclic Amines

Peer reviewed: YesNRC publication: Ye

Photoionization of the iodine 3d, 4s, and 4p orbitals in methyl iodide

Ionization of the I 3d, 4s, and 4p orbitals in methyl iodide (CH$_3$I) has been studied by using synchrotron radiation to measure the total ion yield and by recording photoelectron spectra with linearly polarized radiation in two polarization orientations. The complete photoelectron spectrum of CH3I has been recorded at several photon energies, and bands due to the C 1s, I 3d, 4s, 4p, and 4d atomic-like orbitals, as well as the molecular orbitals, have been observed and assigned. In the vicinity of the I 3d5/2 and 3d3/2 ionization thresholds at 626.8 and 638.3 eV, respectively, the ion yield displays weak structure in the pre-edge region due to transitions into valence or Rydberg states, and, at higher energies, a shoulder and a broad maximum attributed to the I 3d$_{5/2} → εf$ and the I 3d$_{3/2} → εf$ shape resonances, respectively. The absorption spectrum calculated using time-dependent density functional theory, within the Tamm-Dancoff approximation, has allowed assignments to be proposed for the valence and Rydberg states. The Stieltjes imaging technique has been used to simulate the absorption spectrum above the ionization threshold and indicates that transitions into the f(l = 3) continuum channel dominate. This conclusion has been corroborated by a Continuum Multiple Scattering–Xα (CMS–Xα) calculation. The asymmetric broadening of the photoelectron bands associated with the I 3d orbital, due to post collision interaction, is taken into account in our experimental analysis. Experimentally derived photoelectron anisotropy parameters for the I 3d orbital are in good agreement with the theoretical predictions obtained with the CMS–Xα approach. The I 3d shake-up/shake-off photoelectron spectrum has been recorded, and assignments have been proposed for several of the satellites. The M$_4$N$_{45}$N$_{45}$ and M$_5$N$_{45}$N$_{45}$ Auger electron yields have been measured, and that for the M$_5$N$_{45}$N$_{45}$ decay exhibits a maximum due to interchannel coupling between the 3d$_{5/2}$ and 3d$_{3/2}$ continua. The photoelectron band associated with the I 4p orbital has an unusual appearance. Based upon previous theoretical work for the analogous Xe 4p orbital, it appears that the initial I 4p$^{−1}$ hole state decays rapidly through Coster-Kronig and super-Coster-Kronig transitions. This leads to a redistribution of the spectral intensity associated with the I 4p orbital and results in a photoelectron spectrum containing a single structured band together with an extended continuum. Another continuum is observed on the high binding energy side of the peak due to the 4s orbital, and we assign this to super-Coster-Kronig transitions into the 4p$^{-1}$4d$^{−1}$ continuum

High Photon Flux 70 eV HHG Source for Applications in Molecular and Solid State Physics

A 100 kHz high harmonic source with record high >10$^{11}$ photons/s in single harmonics between 55-73 eV is presented. The unique capabilities are underlined by using it for coincidence experiments and measurements on magnetic samples