Probing Surface Information of Alloy by Time of Flight-Secondary Ion Mass Spectrometer

In recent years, time of flight-secondary ion mass spectrometer (ToF-SIMS) has been widely employed to acquire surface information of materials. Here, we investigated the alloy surface by combining the mass spectra and 2D mapping images of ToF-SIMS. We found by surprise that these two results seem to be inconsistent with each other. Therefore, other surface characteristic tools such as SEM-EDS were further used to provide additional supports. The results indicated that such differences may originate from the variance of secondary ion yields, which might be affected by crystal orientation.

Time-resolved relaxation and fragmentation of polycyclic aromatic hydrocarbons investigated in the ultrafast XUV-IR regime

Polycyclic aromatic hydrocarbons (PAHs) play an important role in interstellar chemistry and are subject to high energy photons that can induce excitation, ionization, and fragmentation. Previous studies have demonstrated electronic relaxation of parent PAH monocations over 10–100 femtoseconds as a result of beyond-Born-Oppenheimer coupling between the electronic and nuclear dynamics. Here, we investigate three PAH molecules: fluorene, phenanthrene, and pyrene, using ultrafast XUV and IR laser pulses. Simultaneous measurements of the ion yields, ion momenta, and electron momenta as a function of laser pulse delay allow a detailed insight into the various molecular processes. We report relaxation times for the electronically excited PAH*, PAH+* and PAH2+* states, and show the time-dependent conversion between fragmentation pathways. Additionally, using recoil-frame covariance analysis between ion images, we demonstrate that the dissociation of the PAH2+ ions favors reaction pathways involving two-body breakup and/or loss of neutral fragments totaling an even number of carbon atoms.

The Ion Pair Thermal Model of MALDI MS

The ion pair thermal model for MALDI MS is described. Key elements of the model include thermal desorption and ionization, strong tendency to neutralization via ion pair formation and proton transfer in the gas phase, thermal equilibrium, overall charge neutral plume, and thermal energy assisted free ion generation via ion pair separation by ion extraction potential. The quantities of ions in the solid sample and in the gaseous plume are estimated. Ion yields of different classes of molecules including peptides, nucleic acids, permanent salts and neutral molecules are estimated at the macroscale and single ion pair levels. The estimated ion yields are close to experimentally observed values under certain assumptions. Explanations of several observations in MALDI MS such as mostly single-charged peaks, improvement of spectra by ammonium cation, and ion suppression are provided. We expect that the model can give insights for the design of new conditions and systems for improving the sensitivity and resolution of MALDI MS and improving its capability and reliability to analyze large biomolecules.

Multiple photoionization for the K shell in the Fe atom

Multiple photoionization for the K shell in the Fe atom is studied for all levels of the ground configuration. The study shows that sextuple-photoionization cross sections dominate for all levels of the 3d64s2 configuration. The cross sections strongly depend on the initial level for which the photoionization is investigated. The partial photoionization cross sections to the configurations of the produced ions are determined. The main sequences of the radiative and Auger cascade following the photoionization of the K shell in the Fe atom are identified. Presented ion yields for subconfigurations and levels are compared with the previous calculations for configuration averages, revealing that they strongly overestimate ion yields for the Fe7+–Fe10+ ions.

Single-Photon-Induced Post-Ionization to Boost Ion Yields in MALDI Mass Spectrometry Imaging

Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI) is a rapidly growing method in many fields of the life sciences. For many analyte classes, however, its sensitivity is limited due to poor ionization efficiencies. To mitigate this problem, we here introduce a novel and cost-effective postionization scheme at high repetition rates based on the interplay of single-photon photoionization and subsequent charge transfer reactions. Importantly, the fine vacuum conditions of a dual ion-funnel ion source effectively thermalize the evolving MALDI plume and enable ample gas-phase reactions as well as the addition of chemical dopants that crucially support chemical ionization. Supported by acetone dopant, [M + H]+/[M-H]− signals of numerous glycerophospho-, sphingo-, and further lipids, registered from mammal brain and kidney sections, were boosted by up to three orders of magnitude, similar to results obtained with laser-based postionization (MALDI-2). Experiments utilizing deuterated matrix and dopant, however, indicate complex ionization pathways different from MALDI2.

Ca+ Ions Solvated in Helium Clusters

We present a combined experimental and theoretical investigation on Ca+ ions in helium droplets, HeNCa+. The clusters have been formed in the laboratory by means of electron-impact ionization of Ca-doped helium nanodroplets. Energies and structures of such complexes have been computed using various approaches such as path integral Monte Carlo, diffusion Monte Carlo and basin-hopping methods. The potential energy functions employed in these calculations consist of analytical expressions following an improved Lennard-Jones formula whose parameters are fine-tuned by exploiting ab initio estimations. Ion yields of HeNCa+ -obtained via high-resolution mass spectrometry- generally decrease with N with a more pronounced drop between N=17 and N=25, the computed quantum HeNCa+ evaporation energies resembling this behavior. The analysis of the energies and structures reveals that covering Ca+ with 17 He atoms leads to a cluster with one of the smallest energies per atom. As new atoms are added, they continue to fill the first shell at the expense of reducing its stability, until N=25, which corresponds to the maximum number of atoms in that shell. Behavior of the evaporation energies and radial densities suggests liquid-like cluster structures.

Helium structures around SF5+ and SF6+: A new intermolecular potential and mass sepctrometry experiments

Helium clusters attaching the recently experimentally observed sulphur hexafluoride SF6+ and sulphur pentafluoride SF5+ ions are investigated in a combined experimental and theoretical effort. Mass spectrometry ion yields are obtained...

Multiple Sequential Ionization of Valence n = 4 Shell of Krypton by Intense Femtosecond XUV Pulses

Sequential photoionization of krypton by intense extreme ultraviolet femtosecond pulses is studied theoretically for the photon energies below the 3d excitation threshold. This regime with energetically forbidden Auger decay is characterized by special features, such as time scaling of the level population. The model is based on the solution of rate equations with photoionization cross sections of krypton in different charge and multiplet states determined using R-matrix calculations. Predictions of the ion yields and photoelectron spectra for various photon fluence are presented and discussed.

Multiple photoionization cross sections for Fe2+ K shell

Multiple photoionization cross sections from the K shell are studied for all levels of the Fe2+ 3d6 configuration. The study shows that the quadruple photoionization leads to the largest cross sections. A large variation in the multiple photoionization cross sections is determined among the levels of the Fe2+ 3d6 configuration. Main decay branches of radiative and Auger cascades, following the photoionization of the K shell for the ground configuration of the Fe2+ ion, are identified. The radiative and Auger cascade is studied by considering transitions among energy levels and subconfigurations. The obtained data for ion yields are compared with previous calculations produced for configuration averages.