Dissociative electron attachment (DEA) to diethyl ether yielded primarily the C2H5O− ion, with a strong Feshbach resonance band at 9.1 eV and a weaker shape resonance band at 3.89 eV. Very similar spectra were obtained for dibutyl ether, with C4H9O− bands at 8.0 and 3.6 eV. Some of these primary ions subsequently lost H2 and yielded weaker signals of the C2H3O− and C4H7O− ions. In contrast, DEA to the cyclic ether tetrahydrofuran (THF) yielded mainly a fragment of mass 41, presumably deprotonated ketene, at 7.65 eV. The low-energy band was missing in THF. H− with two bands at 6.88 and 8.61 eV, and an ion of mass 43 (presumably deprotonated acetaldehyde) with two bands at 6.7 and 8.50 eV were also observed. We propose that in the primary DEA step the C–O bond is cleaved in both the open-chain and the cyclic ethers. In the open-chain ethers the excess energy is partitioned between the (internal and kinetic) energies of two fragments, resulting in an RO− ion cool enough to be observed. The ˙CH2(CH2)3O− ion resulting from cleavage of the C–O bond in THF contains the entire excess energy (more than 6 eV at an electron energy of 7.65 eV) and is too short-lived with respect to further dissociation and thermal autodetachment to be detected in a mass spectrometer. These findings imply that there could be a substantial difference between the fragmentation in the gas phase described here and fragmentation in the condensed phase where the initially formed fragments can be rapidly cooled by the environment.
