We consider the influence of resonant laser excitation upon the dissociative reaction between SF6 molecules and very low energy electrons. Experimentally, the use of valence electrons of atoms in Rydberg states ensures a well-defined energy resolution of the scattering electrons in the crossed beam apparatus. A spectroscopic model of the infrared absorption of CO2 laser radiation by SF6 gives a fair determination of the energy levels and vibrational transitions involved in the dissociative process. This reaction between highly excited atoms and a molecule is interpreted as a three step process: attachment of a quasi-free electron, followed by the interaction between the atomic ionic core and the negative molecular ion leading to a partial stabilization and, finally, the competition between the dissociating and the autodetachment channels.

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