Laser ion kinetics: set-up and application of a single-shot femtosecond pump–probe technique

In this contribution the first measurements of a single-shot femtosecond laser pump–probe technique are reported. The technique is based on counter-propagating femtosecond laser pulses in a supersonic beam of a low density of sample molecules and simultaneous probe detection by ion or fragment-ion formation through a reflectron time-of-flight mass spectrometer. It will be shown that the range of the pump–probe delays covers the time span between 100 fs and 10 ps depending on the pulse width of the laser used and the stability of the volt ages of the mass spectrometer. The application of this technique to organometallic compounds as well as to medium-sized organic molecules reveals some insight into the electron-transfer process during ionization through a 1+1 multi-photon absorption procedure. Furthermore it is demonstrated that this technique is also applicable to the investigation of ultra-fast isomerization and fragmentation processes. As an example the results of the processes within iron pentacarbonyl and substituted benzalacetones are reported. Received: 22 October 1999 / Published online: 24 July 2000     

Atom optics and quantum groups

It is shown that in atom optics physical systems arise which have close similarities to quantum group structures. A particular example for which an atomic operator provides a representation of the quantum group GL _q (2,C) forq=−1 is presented.     

Dieisen(III)-hexacyanoferrat(II)-oxid

The title compound3 has been obtained through the action of molecular oxygen upon di-iron(II)-hexacyanoferrate(II)1 which has been prepared by thermal decomposition of ammonium hexacyanoferrate(II)2 in vacuum.2 und3 have been characterized by analytical methods andMössbauer-spectroscopy.3 and the analogous halogen compounds are semiconductors with a conductivity of 2 to 5 · 10^–5 S/cm.2 is ideally suited for the quantitative absorption of oxygen from water and organic solvents.

Herrn Prof. Dres. mult.Viktor Gutmann, Institut für Anorganische Chemie der Technischen Universität Wien, mit besten Wünschen zur Vollendung des 65. Lebensjahres gewidmet.     

Integralsätze bei infinitesimalen Verbiegungen von geschlossenen Raumkurven

Ohne Zusammenfassung     

Multiphoton ionization and photodissociation at the second-order space focus in a time-of-flight mass spectrometer: The amino acid tryptophan

Neutral IR-desorbed molecules of the amino acid tryptophan entrained in a supersonic beam were post-ionized by multiphoton ionization (MUPI) in the gas phase. Variations in the intensity of the ionization laser produced different degrees of fragmentation observed in the time-of-flight mass spectra of tryptophan according to the ladder-switching model for MUPI fragmentation. From the number of absorbed photons the upper values for the appearance energies of specific fragment ions were obtained. A complete fragmentation pathway of tryptophan was established by using photodissociation of molecular ions and fragment ions formed by MUPI. Photodissociation was successfully performed by secondary excitation with a UV laser at the second-order space focus of a reflection time-of-flight instrument. A fragmentation tree for a laser-desorbed molecule obtained in a laser tandem time-of-flight instrument is shown for the first time.     

Design, setup and first results of a miniaturized time-of-flight mass spectrometer with a simple reflector of a new design

A new kind of reflector with only one element has been constructed and used in a miniaturized time-of- flight mass spectrometer. Details from the simulation of the instrument with SIMION and its design are presented and discussed. The instrumental setup is displayed and some first results from measurements are presented. Laser- generated electron ionization (LEI) and resonance-enhanced multi-photon ionization (REMPI) are used for ion production. While both methods yield good mass spectra, the mass resolving power of the instrument is different for both methods. The results of the measurements are compared and discussed with respect to the design. It is found that the resolution of the new instrument is satisfactory for mass spectrometric measurements of small molecules and not limited by the reflector.     

Formation and reactions of clusters in the gas phase: small peptides and carboxylic acids

The cluster formation of seventeen small dipeptides with different primary structures and vanillic acid was investigated by means of a neutral laser desorption and supersonic beam expansion followed by multi photon ionization time of flight mass spectrometry. The structures of these clusters have been characterized by mass spectrometric methods as well as by DFT calculations. It is shown that the structure of the cluster from a dipeptide and vanillic acid is described by a hydrogen bond between the phenolic group of the vanillic acid and the N-terminal amino function of the dipeptide. The intensity of the cluster ion and the main fragmentation product, the protonated peptide ion, can be linked to the proton affinity of the peptide. Furthermore the fragmentation reactions of the protonated peptide are accompanied by extensive hydrogen rearrangements yielding both a and y fragments. The intensities of these fragments follow the proton affinity of the dipeptide.     

Mass analyzed threshold ionization spectroscopy of o-, m-, and p-dichlorobenzenes. Influence of the chlorine position on vibrational spectra and ionization energy

For the first time, vibrational spectra of the 35Cl2 and 35Cl37Cl isotopomers of o-, m-, and p-dichlorobenzene cations in the electronic ground state have been measured via S1 intermediate states by mass analyzed threshold ionization (MATI) spectroscopy. Additionally, ab initio calculations at DFT (density functional theory), CIS (configuration interaction singles), and CASSCF (complete active space self-consistent field) levels of theory have been conducted to compare experimental findings with theory. From the MATI spectra, adiabatic ionization energies of the ortho, meta, and para isomers have been determined to be the same for each pair of investigated isotopomers to 73,237 +/- 6, 72,191 +/- 6, and 73,776 +/- 6 cm(-1), respectively. Several vibrational modes, including fundamentals, combinations, and progressions have been assigned by comparing the experimental and theoretical results. The appearance of overtone progressions involving the 7a mode could be explained by a geometry change of all three isomers during ionization in the direction of this mode by retraining the symmetry of the molecules. Although the general spectral features of the investigated isotopomers are similar, frequencies of some vibrations are slightly different up to a few wavenumbers depending on the involvement of the chlorine atoms in the molecular motion.     

High-resolution mass spectrometry of large molecules in a linear time-of-flight mass spectrometer

This report describes a new high-resolution linear time-of-flight mass spectrometer that has been constructed at this institute. The instrument is used for investigations of both direct and matrix-assisted laser desorption/ionization of large molecules. A unique feature of this new instrument is the incorporation of a 10-cm postsource pulse-focusing region for enhancing the resolution of the detected ion signals. This technique can correct for both high initial ion translational energies and long durations of ion formation and is expected to be particularly well suited for laser desorption/ionization applications. Results of calculations are presented to illustrate the gains in mass resolution that may be expected for a variety of ion formation conditions. In addition, initial experimental results are presented that demonstrate the capability of this new instrument to produce high-resolution ion signals. Signals with mass resolutions as high as 2750 (full width at half maximum) have been obtained for both direct and matrix-assisted laser desorption/ionization signals.