Springer Online Journal Archives 1860-2000
Abstract Searching for oxygen-isotope selectivity, we investigated the infrared multiphoton dissociation of the formaldehyde trimer around 10 µm, in a range where the molecule has a degenerate and a non-degenerate CO stretch vibration and a degenerate CH2 deformation vibration. In the region of the two latter, the wavelength dependence of the dissociation yield exhibits sharp structures. They were assigned ton-photon resonances (n = 2, 3, 5) by the help of the IR spectrum in the fundamental and overtone region. The O and C selectivities were very small (1.05) near the non-degenerate CO stretch band, but surprisingly large (2–4) in the CH2 deformation, which has no isotopic shift. The selectivity is not controlled by the first (n-photon) excitation step, but only by a later step. Its assignment is attempted. The pressure dependence of the dissociation is peculiar: Only after an initial decrease, the yield exhibits the usual rise with pressure. We attribute the decrease to a relaxation which perturbs the two-photon resonance.
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