title: Observation of dihalide elimination upon electron attachment to oxalyl chloride and oxalyl bromide, 300-550 K.
abstract: Rate coefficients have been measured for electron attachment to oxalyl chloride [ClC(O)C(O)Cl] and oxalyl bromide [BrC(O)C(O)Br] in He gas at 133 Pa pressure over the temperature range of 300-550 K. With oxalyl chloride, the major ion product of attachment is Cl2(-) at all temperatures (66% at 300 K); its importance increases slightly as temperature increases. Two other product ions formed are Cl- (18% at 300 K) and the phosgene anion CCl2O- (16% at 300 K) and appear to arise from a common mechanism. With oxalyl bromide, the Br2(-) channel represents almost half of the ion product of attachment, independent of temperature. Br- accounts for the remainder. For oxalyl chloride, the attachment rate coefficient is small [(1.8 +/- 0.5) x 10(-8) cm3 s(-1) at 300 K], and increases with temperature. The attachment rate coefficient for oxalyl bromide [(1.3 +/- 0.4) x 10(-7) cm3 s(-1) at 300 K] is nearly collisional and increases only slightly with temperature. Stable parent anions C2Cl2O2(-) and C2Br2O2(-) and adduct anions Cl- (C2Cl2O2) and Br- (C2Br3O2) were observed but are not primary attachment products. G2 and G3 theories were applied to determine geometries of products and energetics of the electron attachment and ion-molecule reactions studied. Electron attachment to both oxalyl halide molecules leads to a shorter C-C bond and longer C-Cl bond in the anions formed. Trans and gauche conformers of the neutral and anionic oxalyl halide species have similar energies and are more stable than the cis conformer, which lies 100-200 meV higher in energy. For C2Cl2O2, C2Cl2O2(-), and C2Br2O2(-), the trans conformer is the most stable conformation. The calculations are ambiguous as to the oxalyl bromide geometry (trans or gauche), the result depending on the theoretical method and basis set. The cis conformers for C2Cl2O2 and C2Br2O2 are transition states. In contrast, the cis conformers of the anionic oxalyl halide molecules are stable, lying 131 meV above trans-C2Cl2O2(-) and 179 meV above trans-C2Br2O2(-). Chien et al. [J. Phys. Chem. A 103, 7918 (1999)] and Kim et al. [J. Chem. Phys. 122, 234313 (2005)] found that the potential energy surface for rotation about the C-C bond in C2Cl2O2 is "extremely flat." Our computational data indicate that the analogous torsional surfaces for C2Br2O2, C2Cl2O2(-), and C2Br2O2(-) are similarly flat. The electron affinity of oxalyl chloride, oxalyl bromide, and phosgene were calculated to be 1.91 eV (G3), and 2.00 eV (G2), and 1.17 eV (G3), respectively.
authors.affiliation: Department of Chemistry, College of the Holy Cross, Worcester, Massachusetts 01610-2395, USA. jvandoren@holycross.edu
authors.forename: Jane M
authors.initials: JM
authors.lastname: Van Doren
authors.forename: Kathleen B
authors.initials: KB
authors.lastname: Hogan
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Miller
authors.forename: A A
authors.initials: AA
authors.lastname: Viggiano