INFRARED PHOTODISSOCIATION SPECTROSCOPY OF $M^{+}-(C_{2}H_{2})_{n})$ $CLUSTERS^{a}$

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2002

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Ohio State University

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Metal ion-acetylene complexes of the general form $M^{+}-(C_{2}H_{2})_{n}$ are synthesized in the gas phase by a pulsed nozzle laser ablation cluster source. These ions are then mass selected in a reflectron time-of-flight mass spectrometer where they are excited and undergo multiphoton absorption from a tunable infrared OPO/OPA laser system. Efficient fragmentation occurs by the loss of whole $C_{2}H_{2}$ units and this process is enhanced on vibrational resonances near the symmetric and asymmetric C-H stretch frequencies of acetylene. Infrared photofragmentation spectra are obtained by monitoring the fragment yield versus energy of the tunable infrared laser in the $3000 cm^{-1}$ to $3400 cm^{-1}$ region. the observed infrared band positions are red-shifted from those of free acetylene consistent with the weakening of the carbon-carbon bond energy by $\pi$ electron withdrawal. Interpretation of the spectra for $M^{+} = Ni^{+}$ and $Co^{+}$ will be discussed.

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$^{a}$Research sponsored by the U.S. Department of Energy
Author Institution: Department of Chemistry, University of Georgia

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