Faculté des sciences

Experimental evidence on the mechanism of dissociative electron attachment to formic acid

Janečková, Radmila ; Kubala, Dušan ; May, Olivier ; Fedor, Juraj ; Allan, Michael

In: Physical Review Letters, 2013, vol. 111, no. 21, p. 213201

Two mechanisms for dissociative electron attachment in HCOOH, the formation of HCOO−+H, were proposed in the literature: (i) via a direct electron attachment into a σ∗ resonance, augmented by dipole binding of the incident electron [G. A. Gallup et al., Phys. Rev. A 79, 042701 (2009)], and (ii) with the 1.8 eV π∗ resonance as a doorway state, linked to the products by... More

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    Summary
    Two mechanisms for dissociative electron attachment in HCOOH, the formation of HCOO−+H, were proposed in the literature: (i) via a direct electron attachment into a σ∗ resonance, augmented by dipole binding of the incident electron [G. A. Gallup et al., Phys. Rev. A 79, 042701 (2009)], and (ii) with the 1.8 eV π∗ resonance as a doorway state, linked to the products by symmetry lowering–distortion of the temporary anion, primarily the CH bond, from the planar symmetry [T. N. Rescigno et al., Phys. Rev. Lett. 96, 213201 (2006)]. The later mechanism implies a reduction of the cross section upon deuteration of the hydrogen bonded to the C atom, whereas the former mechanism would leave the cross section unaffected. Our experimental absolute cross sections for the four isotopomers of formic acid show that deuteration on the C atom reduces the cross section value only marginally (by 12%) compared to deuteration on the O atom (reduction by a factor of 16), and thus favor mechanism (i).