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

• Published in: Chemphyschem Vol. 22; no. 13; pp. 1316 - 1320
• Main Authors: Corkish, Timothy R., Haakansson, Christian T., Watson, Peter D., Robinson, Hayden T., McKinley, Allan J., Wild, Duncan A.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 02.07.2021
• Subjects: ab initio calculations; Carbonyls; electronic structure; Electropositivity; halides; noncovalent interactions; photoelectron spectroscopy; Photoelectrons; Solvation; Photoelectron Spectroscopy; Ab initio calculations; noncovalent interactions; halides; electronic structure
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.202100180

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. All about halide interactions: Fundamental ion solvation in the gas phase has been investigated via noncovalent complexes consisting of halide anions and CH3CHO and CD3CDO. This study delves into the interactions between halide anions and small carbonyl‐containing molecules, uncovering molecular structures and electronic trends.