A combined experimental and theoretical approach has been used to study intermolecular chalcogen bonding. Specifically, the chalcogen bonding occurring between halide anions and CS2 molecules has been investigated using both anion photoelectron spectroscopy and high‐level CCSD(T) calculations. The relative strength of the chalcogen bond has been determined computationally using the complex dissociation energies as well as experimentally using the electron stabilisation energies. The anion complexes featured dissociation energies on the order of 47 kJ/mol to 37 kJ/mol, decreasing with increasing halide size. Additionally, the corresponding neutral complexes have been examined computationally, and show three loosely‐bound structural motifs and a molecular radical.

A combined experimental and theoretical approach has been used to investigate X−⋅⋅⋅CH2O (X=F, Cl, Br, I) complexes in the gas phase. Photoelectron spectroscopy, in tandem with time‐of‐flight mass spectrometry, has been used to determine electron binding energies for the Cl−⋅⋅⋅CH2O, Br−⋅⋅⋅CH2O, and I−⋅⋅⋅CH2O species. Additionally, high‐level CCSD(T) calculations found a C2v minimum for these three anion complexes, with predicted electron detachment energies in excellent agreement with the experimental photoelectron spectra. F−⋅⋅⋅CH2O was also studied theoretically, with a Cs hydrogen‐bonded complex found to be the global minimum. Calculations extended to neutral X⋅⋅⋅CH2O complexes, with the results of potential interest to atmospheric CH2O chemistry.

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The anion photoelectron spectra of Cl−⋅⋅⋅CD3CDO, Cl−⋅⋅⋅(CD3CDO)2, Br−⋅⋅⋅CH3CHO, and I−⋅⋅⋅CH3CHO are presented with electron stabilisation energies of 0.55, 0.93, 0.48, and 0.40 eV, respectively. Optimised geometries of the singly solvated species featured the halide appended to the CH3CHO molecule in‐line with the electropositive portion of the C=O bond and having binding energies between 45 and 52 kJ mol−1. The doubly solvated Cl−⋅⋅⋅(CH3CHO)2 species features asymmetric solvation upon the addition of a second CH3CHO molecule. Theoretical detachment energies were found to be in excellent agreement with experiment, with comparisons drawn between other halide complexes with simple carbonyl molecules.

Anion photoelectron spectroscopy has been used to determine the electron binding energies of the X-···C3H6 (X = Cl, Br, I) complexes. To complement the experimental spectra the DSD-PBEP86-D3BJ functional has...