INFRARED SPECTRA OF $CH_{3}^{+}$ -$Rg_{n}$), COMPLEXES ($Rg=He, Ne, Ar, n=1,2$)

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1999

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Ohio State University

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Rotationally resolved infrared photodissociation spectra of CH3+-Rgn ionic complexers (Rg = He,Ne,Ar, n=1,2), have been recorded in a tendem mass spectrometer. The spectra of the dimers are compatible with π--bonded equilibrium structures where the Rg atoms are attached to the vacant 2pz orbital of the central C atom (C3v symmetry). In the case of Ar, partial charge transfer into this orbital leads to a large binding energy of the complex (ca. 0.5 eV), so that only overtones of the CH stretch modes can be observed in the photofragmentation spectra. The strong intermolecular bond induces a massive deformation of the CH3+ ion which transforms from sp2 towards sp3 hybridization. In the ArCH3+-Ar trimer the second Ar atom is weakly attached to the other side of the 2pz orbital of C (C3v symmetry). The two C-Ar bonds are not equivalent: one is strong and short, the other one is long and weak. However, tunneling splittings reveal that they can exchange their role via the intracluster inversion motion of CH3+ through a transition state with D3h symmetrya. The intermolecular bonds in the He and Ne containing complexes are much weaker and result mainly from induction interactions. The CH3+ deformation is smaller and the absence of the tunneling splittings in the NeCH3+-Ne spectrum suggests that the trimers have D3h equilibrium geometries. The experimental results are supported by ab initio calculations.

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a R. V. Olkhov, S. A. Nizkorodov and O. Dopfer J. Chem. Phys. 108, 10046, 1998.


Author Institution: Institute for Physical Chemistry, University of Basle

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