Abstract
We report infrared photodissociation spectra for Ne, Ar, Kr, N2 and CH4 clusters which contain CH3F chromophores. The CH3Fv 3 mode is excited with a line tunable CO2 laser. Mass spectrometer detection of changes in the cluster beam intensity serve to partially distinguish the spectra of different size neutral clusters. Many spectra consist of rather broad, inhomogeneous profiles. For intermediate size ArnCH3F clusters a sharp, narrow peak is observed in the spectrum. We assign this peak as due to a cluster in which a central CH3F molecule is surrounded by at least a full shell of Ar atoms packed in a contracted icosohedral geometry. Because the Ar atoms in a gas phase cluster are unconstrained by an extended crystalline structure, the CH3F dipole is more fully stabilized (and thus red-shifted) than in a solid matrix. The dependence of the observed spectrum on cluster size is discussed. For comparison, no comparable narrow spectral features are observed in ArnC2H4 cluster spectra. Clear evidence is also presented that the fragmentation of the neutral clusters upon electron impact ionization is fairly specific. Finally, we note that ionization of ArnCH3F clusters sometimes produces ArnF+ ions. This is a fragmentation process which does not occur in free CH3F.
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