Abstract

The photodissociation dynamics of acetylene to hydrogen atoms, C 2H 2 → C 2H + H and C 2D 2 → C 2D + D, with C 2H and C 2D in the ground X ̃ 2 Σ + and/or excited electronic A ̃ 2 Π states, has been investigated for the first time with tunable narrow-band vacuum ultraviolet laser radiation between 121 and 133 nm by employing hydrogen atom photofragment action spectroscopy. Action spectra have been taken at 2.5 cm −1 resolution with acetylene in a molecular beam adiabatically cooled internally to about 4 K. They exhibit pronounced discrete predissociative resonances of Rydberg and valence excited states resolved to homogeneous widths. From them dissociation lifetimes of individual states from 5 × 10 −14 s to longer than 2 × 10 −12 s are derived.

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