Towards an Understanding of Halide Interactions with the Carbonyl‐Containing Molecule CH3CHO

The anion photoelectron spectra of of Cl - ⋯CD 3 CDO, Cl - ⋯(CD 3 CDO) 2 , Br - ⋯CH 3 CHO, and I - ⋯CH 3 CHO are presented with respective electron stabilisation energies of 0.55 eV, 0.93 eV, 0.48 eV, and 0.40 eV. Optimised geometries of the singly solvated species featured the halide appended to the CH 3 CHO molecule in-line with the electropositive portion of the C=O bond and have binding energies between 45 and 52 kJ mol -1 . The doubly solvated Cl - ⋯(CH 3 CHO) 2 species features asymmetric solvation upon the addition of a second CH 3 CHO molecule. Theoretical detachment energies were found to be in excellent agreement with experiment, with comparisons drawn between other halide complexes with simple carbonyl molecules.