Anion of Oxalyl Chloride: Structure and Spectroscopy.

The structure and spectroscopy of the anion of oxalyl chloride are investigated using photoelectron imaging experiments and ab initio modeling. The photoelectron images, spectra, and angular distributions are obtained at 355 and 532 nm wavelengths. The 355 nm spectrum consists of a band assigned to a transition from the ground state of the anion to the ground state of the neutral. Its onset at ∼1.8 eV corresponds to the adiabatic electron affinity (EA) of oxalyl chloride, in agreement with the coupled-cluster calculations predicting an EA of 1.797 eV. The observed vertical detachment energy, 2.33(4) eV, is also in agreement with the theory predictions. The 532 nm spectrum additionally reveals a sharp onset near the photon-energy limit. This feature is ascribed to autodetachment via a low-energy anionic resonance. The results are discussed in the context of the substitution series, which includes glyoxal, methylglyoxal (single methyl substitution), biacetyl (double methyl substitution), and oxalyl chloride (double chlorine substitution). The EAs and anion detachment energies follow the trend: biacetyl < methylglyoxal < glyoxal ≪ oxalyl chloride. The electron-donating character of the methyl group has a destabilizing effect on the substituted anions, reducing the EA from glyoxal to methylglyoxal to biacetyl. In contrast, the strong electron-withdrawing (inductive) power of Cl lends additional stabilization to the oxalyl chloride anion, resulting in a large (∼1 eV) increase in its detachment energy compared to glyoxal.