Dissociative electron attachment in alcohols and ethers: Its relatioship to Rydberg states

A dramatic difference was observed in the reactivity of alcohols and ethers toward free electrons. Whereas the lowest core-excited state of the negative ion - a 2(n,3s2) Feshbach resonance - of the alcohols readily dissociates by losing a hydrogen atom, ethers show no observable signal from this resonance. This difference in reactivity has a parallel in the anomalous shapes and energies of the parent states of the Feshbach resonances, the 1(n,3s) Rydberg states of the neutral alcohols and ethers. We explained this anomaly by means of potential surfaces of the alcohols and ethers calculated using the TD-DFT method as a function of the dissociation coordinate. The lowest excited state of alcohols was found to be repulsive, as a consequence of an avoided crossing between the 3s and 3px Rydberg configurations, whereas a barrier to dissociation was found in the ethers. Rydberg-valence mixing and avoided crossings are decisive in determining the shapes of the potential surfaces. It is concluded that the reactivities of alcohols and ethers toward free electrons are rationalized by assuming that the potential surfaces of the daughter Feshbach resonances closely follow those of the parent Rydberg states, i.e., the lowest Feshbach resonance is repulsive, but a barrier occurs in ethers. The potential surfaces of both the Rydberg states and the Feshbach resonances thus differ dramatically from the non-dissociative surface of the grandparent 2(n-1) positive ions, despite the nominally non-bonding character of the Rydberg electrons.