Anion Photoelectron Spectra and Ab Initio Calculations of the Iodide–Carbon Monoxide Clusters: I^–···(CO)_n, n = 1–4

Abstract

Anion photoelectron spectra are reported for the iodide-carbon monoxide clusters, with supporting ab initio calculations for the 1:1 dimer anion and neutral complexes. A C(s) minimum geometry is predicted for the anion complex, while for the neutral complex two linear van der Waals minima are predicted differing in the attachment point of the iodine, that is, I···CO and I···OC. The predicted adiabatic photodetachment energy agrees well with the experimental spectrum. The photoelectron spectra feature a vibrational progression in the CO stretching mode, which becomes more pronounced for the larger clusters.

Sneaking up on the Criegee intermediate from below: Predicted photoelectron spectrum of the CH2OO− anion and W3-F12 electron affinity of CH2OO

“…Our laboratory has also recently made contributions in this area. [22][23][24] To the best of the authors' knowledge, there have been no previous computational or experimental investigations of the CH 2 OOanion. A computational study by Roos and co-workers deals with the dioxyrane, dioxymethane, and the dioxymethane anion, 25 however the dioxymethane species have both oxygen atoms bound to carbon and not to each other, while for dioxyrane there is an O−O bond.…”

Halide–Nitrogen Gas-Phase Clusters: Anion Photoelectron Spectroscopy and High Level ab Initio Calculations

“…Compared with the halide–carbon monoxide species reported previously by our group, the halide–nitrogen set displays similar stabilization energies which can be rationalized by considering that the predicted D 0 values of 9.9 and 7.3 kJ mol –1 for the bromide and iodide–carbon monoxide complexes are close to those predicted for bromide and iodide–N 2 . The stabilization energies are also very similar, being 140 and 90 meV for bromide and iodide–CO, respectively. , …”

“…The stabilization energies are also very similar, being 140 and 90 meV for bromide and iodide−CO, respectively. 36,37…”

Noncovalent chalcogen and tetrel bonding interactions: Spectroscopic study of halide–carbonyl sulfide complexes

“…Presumably, this shortening of the CO bond results in the vibrational progression associated with the C=O stretch observed in the iodide‐carbonyl sulfide anion photoelectron spectra. In order to rationalize the relative enhancement observed in the vibrational progression upon solvation of additional carbonyl sulfide molecules around the iodide anion core, attention is focussed to similar photoelectron spectra associated with iodide complexes containing both carbon monoxide and carbon dioxide 93,94 . In particular, these studies found vibrational progression associated with the OCO bend and the C=O stretch increased in intensity upon increasing solvation number around the iodide, and this was attributed to the photodetachment event collectively exciting the in‐phase vibration in each respective solvating molecule 93,94 .…”

“…In order to rationalize the relative enhancement observed in the vibrational progression upon solvation of additional carbonyl sulfide molecules around the iodide anion core, attention is focussed to similar photoelectron spectra associated with iodide complexes containing both carbon monoxide and carbon dioxide 93,94 . In particular, these studies found vibrational progression associated with the OCO bend and the C=O stretch increased in intensity upon increasing solvation number around the iodide, and this was attributed to the photodetachment event collectively exciting the in‐phase vibration in each respective solvating molecule 93,94 . In the context of carbonyl sulfide, this increase in vibrational progression intensity upon solvation suggests that each carbonyl sulfide molecule is bound in an equivalent fashion, allowing a collective in‐phase vibration to occur.…”