A dramatic difference between the electron-driven dissociation of alcohols and ethers and its relation to Rydberg states

A 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. We explained this anomaly using 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, 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

Cleavage of the ether bond by electron impact: differences between linear ethers and tetrahydrofuran

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

Absolute cross sections for dissociative electron attachment to acetylene and diacetylene

Absolute cross sections for the production of the two astronomy-relevant negative ions H−C≡C⁻ and H−C≡C−C≡C⁻ by dissociative electron attachment to acetylene C₂H₂ and diacetylene C₄H₂ were measured (with a ±25% error bar). Acetylene yielded the C₂H⁻ ion at an electron energy of 2.95  eV with a cross section of 3.6±0.9  pm² and also the C₂⁻ ion at 8.1  eV with a cross section of 4.1±1  pm². Diacetylene yielded the C₄H⁻ ion at 2.5  eV with a cross section of 3.0±0.8  pm² and at 5.25  eVwith a cross section of 73±17  pm². Weaker C ₄⁻ C₂H⁻, and C₂⁻ signals were also observed from diacetylene. The identity of the negative ion resonances mediating the dissociation and the consequences for the production of these ions in discharges are discussed. An alternate path for C₄H⁻ formation, from the O⁻-C₄H₂ ion-molecule reaction, was also observed

Electron-induced chemistry of alcohols

We studied dissociative electron attachment to a series of compounds with one or two hydroxyl groups. For the monoalcohols we found, apart from the known fragmentations in the 6–12 eV range proceeding via Feshbach resonances, also new weaker processes at lower energies, around 3 eV. They have a steep onset at the dissociation threshold and show a dramatic D/H isotope effect. We assigned them as proceeding via shape resonances with temporary occupation of σ*O–H orbitals. These low energy fragmentations become much stronger in the larger molecules and the strongest DEA process in the compounds with two hydroxyl groups, which thus represent an intermediate case between the behavior of small alcohols and the sugar ribose which was discovered to have strong DEA fragmentations near zero electron energy [S. Ptasińska, S. Denifl, P. Scheier and T. D. Märk, J. Chem. Phys., 2004, 120, 8505]. Above 6 eV, in the Feshbach resonance regime, the dominant process is a fast loss of a hydrogen atom from the hydroxyl group. In some cases the resulting (M– 1)⁻ anion (loss of hydrogen atom) is sufficiently energy-rich to further dissociate by loss of stable, closed shell molecules like H₂ or ethene. The fast primary process is state- and site selective in several cases, the negative ion states with a hole in the nO orbital losing the OH hydrogen, those with a hole in the σC–H orbitals the alkyl hydrogen

Absolute angle-differential vibrational excitation cross sections for electron collisions with diacetylene

Absolute vibrational excitation cross sections were measured for diacetylene (1,3-butadiyne). The selectivity of vibrational excitation reveals detailed information about the shape resonances. Excitation of the C≡C stretch and of double quanta of the C-H bend vibrations reveals a ²Πu resonance at 1 eV (autodetachment width ~30 meV) and a ²Πg resonance at 6.2 eV (autodetachment width 1–2 eV). There is a strong preference for excitation of even quanta of the bending vibration. Excitation of the C-H stretch vibration reveals σ* resonances at 4.3, 6.8, and 9.8 eV, with autodetachment widths of ~2 eV. Detailed information about resonances permits conclusions about the mechanism of the dissociative electron attachment