Vibrational Spectroscopy and Density Functional Theory of Transition-Metal Ion−Benzene and Dibenzene Complexes in the Gas Phase

Metal−benzene complexes of the form M(benzene) n (M = Ti, V, Fe, Co, Ni) are produced in the gas-phase environment of a molecular beam by laser vaporization in a pulsed nozzle cluster source. These complexes are photoionized with an ArF excimer laser, producing the corresponding cations. The respect...

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Veröffentlicht in:Journal of the American Chemical Society 2004-09, Vol.126 (35), p.10981-10991
Hauptverfasser: Jaeger, Todd D, van Heijnsbergen, Deniz, Klippenstein, Stephen J, von Helden, Gert, Meijer, Gerard, Duncan, Michael A
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container_end_page 10991
container_issue 35
container_start_page 10981
container_title Journal of the American Chemical Society
container_volume 126
creator Jaeger, Todd D
van Heijnsbergen, Deniz
Klippenstein, Stephen J
von Helden, Gert
Meijer, Gerard
Duncan, Michael A
description Metal−benzene complexes of the form M(benzene) n (M = Ti, V, Fe, Co, Ni) are produced in the gas-phase environment of a molecular beam by laser vaporization in a pulsed nozzle cluster source. These complexes are photoionized with an ArF excimer laser, producing the corresponding cations. The respective mono- and dibenzene complex ions are isolated in an ion-trap mass spectrometer and studied with infrared resonance enhanced multiple-photon dissociation (IR-REMPD) spectroscopy using a tunable free electron laser. Photodissociation of all complexes occurs by the elimination of intact neutral benzene molecules, and this process is enhanced on resonances in the vibrational spectrum, making it possible to measure vibrational spectroscopy for size-selected complexes. Vibrational bands in the 600−1700 cm-1 region are characteristic of the benzene molecular moiety with systematic shifts caused by the metal bonding. The spectra in this solvent-free environment exhibit periodic trends in band shifts and intensities relative to the free benzene molecule that varies with the metal. Density functional theory calculations are employed to investigate the structures, energetics, and vibrational frequencies of these complexes. The comparison between experiment and theory provides fascinating new insight into the bonding in these prototypical organometallic complexes.
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subjects Atomic and molecular physics
Diffuse spectra
predissociation, photodissociation
Exact sciences and technology
Molecular properties and interactions with photons
Photon interactions with molecules
Physics
title Vibrational Spectroscopy and Density Functional Theory of Transition-Metal Ion−Benzene and Dibenzene Complexes in the Gas Phase
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