Enhanced electron attachment to superexcited states of saturated tertiary amines

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Abstract
Electron attachment measurements on excimer–laser‐excited superexcited states (SES) of saturated amine compounds, and in particular on triethylamine (TEA), have been carried out employing a new experimental technique. A rate equation analysis based on a proposed model shows that the electron attachment rate constant for the SES is several orders of magnitude larger than that for the ground electronic state. The proposed mechanism for electron attachment to SES involves the capture of a near‐zero‐energy electron—(produced by the same laser pulse that produces the SES)—by a superexcited molecule to form a transient parent anion which subsequently dissociates producing a stable fragment anion. The similarity of the above mechanism to an electron‐excited Feshbach resonance is indicated and a scheme for the identification of molecular systems that can be excited (via resonance‐enhancedmultiphoton excitation) to SES is outlined.

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