INFRARED SPECTRUM OF THE $\nu_{3}$ BAND OF $CH_{3}^{+}$

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1986

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Ohio State University

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We have observed1 the vibration-rotation spectrum of the ν3 band of CH3+. This ion was produced both in air-cooled and water-cooled discharge cells with a gas mixture of He:H2:CH4 (700:20:1) with a total pressure of ≈7 Torr. The spectrum was observed using a difference frequency laser system combined with velocity modulation. The spectrum appeared in the same region as that of C2H3+, but intensity variation with chemistry made it possible to discriminate lines of the two species. About 150 lines have been measured and assigned. An extensive analysis was done using the symmetric rotor Hamiltonian with l-resonance and higher order effects, i.e.A1A2 splitting. The spectral pattern clearly indicates that the geometrical structure of CH3+ has D3h symmetry as anticipated by theory. The following preliminary fundamental vibration-rotation constants have been obtained (in cm−1): ν0+34ηk=3106.53995(980)B0=9.36208(26)C0=4.61252B=9.27448(63)C=4.56959Cζ33=0.52025 In separating Cζ33 from C, we used a calculated inertial defect of Δo=0.0535 amu\AA2.

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1 Mark W. Crofton et al., J. Chem. Phys., 83, 3702 (1985). Address of Crofton, Jagod, Rehfuss, and Oka: Department of Chemistry and Department of Astronomy and Astrophysics, The University of Chicago, Chicago, Illinois 60637. Address of Kreiner: Department of Physical Chemistry, University of Ulm, Ulm, Federal Republic of Germany.


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