Parent anion radical formation in coenzyme Q0: Breaking ubiquinone family rules.

We report electron attachment (EA) measurements for the parent anion radical formation from coenzyme Q0 (CoQ0) at low electron energies (<2 eV) along with quantum chemical calculations. CoQ0 may be considered a prototype for the electron withdrawing properties of the larger CoQ n molecules, in particular ubiquinone (CoQ10), an electron carrier in aerobic cell respiration. Herein, we show that the mechanisms for the parent anion radical formation of CoQ0 and CoQ n (n = 1,2,4) are remarkably distinct. Reported EA data for CoQ1, CoQ2, CoQ4 and para-benzoquinone indicated stabilization of the parent anion radicals around 1.2-1.4 eV. In contrast, we observe for the yield of the parent anion radical of CoQ0 a sharp peak at âˆ¼ 0 eV, a shoulder at 0.07 eV and a peak around 0.49 eV. Although the mechanisms for the latter feature remain unclear, our calculations suggest that a dipole bound state (DBS) would account for the lower energy signals. Additionally, the isoprenoid side chains in CoQ n (n = 1,2,4) molecules seem to influence the DBS formation for these compounds. In contrast, the side chains enhance the parent anion radical stabilization around 1.4 eV. The absence of parent anion radical formation around 1.4 eV for CoQ0 can be attributed to the short auto-ionization lifetimes. The present results shed light on the underappreciated role played by the side chains in the stabilization of the parent anion radical. The isoprenoid tails should be viewed as co-responsible for the electron-accepting properties of ubiquinone, not mere spectators of electron transfer reactions.

Hexachlorobenzene-negative ion formation in electron attachment experiments.

In this contribution, we report a comprehensive study on the formation of hexachlorobenzene (C6Cl6) negative ions probed by low-energy electron interactions from 0 up to 12 eV in a gas-phase crossed beam experiment. The anionic yields as a function of the electron energy reveal a rich fragmentation pattern of the dissociative electron attachment process, yet the most intense ion has been assigned to the non-dissociated parent anion that survives long enough within the detection time window. Other less intense fragment anions have been assigned as Cl-, Cl2-, C6Cl4-, and C6Cl5-. The experimental results are accompanied by quantum chemical calculations at various levels of accuracy, providing an insight into the electronic structure, thermochemical thresholds, electron affinities and structures of neutral and anionic molecular species. The electron attachment process induces a considerable geometry change in the temporary-negative ion relative to the neutral molecule, where the most intense fragment anion assigned to Cl- can be formed solely through a curve crossing involving a π*/σ* coupling. The yield of chlorine anions shows a signature of vibrational excitation reminiscent of a Jahn-Teller distortion.