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- Kurzbeschreibung"Progress in Physical Chemistry" is a collection of recent "Review Articles" published in the "Zeitschrift für Physikalische Chemie". The aim of a "Review Article" is to give a profound survey on a special topic outlining the history, development, state of the art and future research. Collecting these Reviews the Editor(s) of "Zeitschrift für Physikalische Chemie" intend to counteract the expanding flood of papers and thereby to give students and researchers a means to obtain fundamental knowledge on their special interests. The first volume of "Progress in Physical Chemistry" is mainly focussed on intermolecular interaction, also glancing at topics that are marginally touched. Contents: M. Havenith*, G. W. Schwaab, Attacking a Small Beast: Ar-Co, a Proto-type for Intermolecular Forces; O. Dopfer, IR Spectroscopy of Microsolvated Aromatic Cluster Ions: Ionization-Induced Switch in Aromatic Molecule-Solvent Recognition; C. F. Kaminski, Fluorescence Imaging of Reactive Processes; T. Stangler, R. Hartmann, D. Willbold, B. W. König*, Modern High Resolution NMR for the Study of Structure, Dynamics and Interactions of Biological Macromolecules; M. Drescher, Time-Resolved ESCA: a Novel Probe for Chemical Dynamics; C. Donner: Kinetics of Electrochemical Phase Formation in Two-Dimensional Systems; C. Czeslik, Factors Ruling Protein Adsorption; T. Kopp, Homogeneous Ice Nucleation in Water and Aqueous Solutions
- AutorHelmut Baumgärtel
- HerausgaberHelmut Baumgärtel
- VerlagOldenbourg Wissenschaftsverlag
- FormatGebundene Ausgabe
- Seiten284 Seiten
- Gewicht720 g
- LeseprobeIR Spectroscopy of Microsolvated Aromatic Cluster Ions: Ionization-Induced Switch in Aromatic Molecule Solvent Recognition (S. 39-40)
By Otto Dopfer
Institut für Physikalische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany
Ion Ligand Interaction / IR Spectroscopy / Cluster Ions / Ion Solvation / Aromatic Molecules
IR spectroscopy, mass spectrometry, and quantum chemical calculations are employed to characterize the intermolecular interaction of a variety of aromatic cations (A+) with several types of solvents. For this purpose, isolated ionic complexes of the type A+ Ln , in which A+ is microsolvated by a controlled number (n) of ligands (L), are prepared in a supersonic plasma expansion, and their spectra are obtained by IR photodissociation (IRPD) spectroscopy in a tandem mass spectrometer. Two prototypes of aromatic ion solvent recognition are considered: (i) microsolvation of acidic aromatic cations in a nonpolar hydrophobic solvent and (ii) microsolvation of bare aromatic hydrocarbon cations in a polar hydrophilic solvent.
The analysis of the IRPD spectra of A+ L dimers provides detailed information about the intermolecular interaction between the aromatic ion and the neutral solvent, such as ion ligand binding energies, the competition between different intermolecular binding motifs (H-bonds, p-bonds, charge dipole bonds), and its dependence on chemical properties of both the A+ cation and the solvent type L. IRPD spectra of larger A+ Ln clusters yield detailed insight into the cluster growth process, including the formation of structural isomers, the competition between ion solvent and solvent solvent interactions, and the degree of (non)cooperativity of the intermolecular interactions as a function of solvent type and degree of solvation. The systematic A+ Ln cluster studies are shown to reveal valuable new information about fundamental chemical properties of the bare A+ cation, such as proton affinity, acidity, and reactivity.
Because of the additional attraction arising from the excess charge, the interaction in the A+ Ln cation clusters differs largely from that in the corresponding neutral A Ln clusters with respect to both the interaction strength and the most stable structure, implying in most cases an ionization-induced switch in the preferred aromatic molecule solvent recognition motif. This process causes severe limitations for the spectroscopic characterization of ion ligand complexes using popular photoionization techniques, due to the restrictions imposed by the Franck Condon principle
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