Publication
The Journal of Chemical Physics
Paper

Infrared-ultraviolet double resonance studies of benzene molecules in a supersonic beam

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Abstract

We have used IR excitation to selectively create populations in admixtures of the zeroth-order states comprising the ∼3000 cm-1 "C-H stretching Fermi triad" of benzene. UV spectra of the 260 nm Ä( 1B2u) → X̃(1A1g) transition in the IR-excited molecules show several new bands, which we have assigned. Final states in the UV transitions are some vibrational levels which have not been detected before, allowing us to find several excited-state vibrational frequencies. We have determined ν3′ = 1327 ± 3 cm-1, ν19′ = 1405 ± 3 cm -1, and ν20′ = 3084 ± 5 cm-1. Also, vibrational structure which was unresolved in IR spectra of the "Fermi triad" was resolved in the UV double resonance spectra, confirming that the C-H stretching admixture is really a tetrad. The 3048, 3079, and 3101 cm-1 states had formerly been given the labels ν20″, ν8″ + ν19″, and ν1″ + ν6″ + ν19″ , respectively. Actually, the middle level most nearly resembles ν1″ + ν6″ + ν19″, and the 3101 cm-1 level is strongly mixed with ν 3″ + ν6″ + ν5″. As predicted by molecular orbital theory, excited-state C-H bending and stretching frequencies are not very different from those in the ground state. Furthermore, we suggest that the four C-H stretching frequencies increase uniformly by ∼20 cm-1 in the excited state; reexamination of the Atkinson and Parmenter 260 nm à ← X̃ spectrum leads us to reassign ν2′ from 3130 to ∼3093 cm-1, which is 19 cm-1 above ν2″. There is a Fermi resonance between the ν6′ + ν20′ level and another level ∼ 13 cm-1 lower in energy; the strength of the perturbation is ∼ 18 cm-1. Possibilities for the perturbing vibrational state are ν6′ + ν8′ + ν14′ and ν6′ + ν13′. © 1988 American Institute of Physics.

Date

01 Jan 1988

Publication

The Journal of Chemical Physics

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