The bromide-bromomethyl radical dimer complex: Anion photoelectron spectroscopy and CCSD(T) calculations

Haakansson, Christian T.; Corkish, Timothy R.; Watson, Peter D.; McKinley, Allan J.; Wild, Duncan A.

doi:10.1016/j.cplett.2020.138060

Cited by 10 publications

(18 citation statements)

References 43 publications

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“…[30][31][32] Details associated with the experimental and computational methods have been provided in the Supporting Information. The relative agreement between calculated electron binding energies and their experimental counterparts has been established in previous publications, [26,[32][33][34][35] and will be reiterated in the current work.…”

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confidence: 79%

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

et al. 2021

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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.

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confidence: 79%

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

et al. 2021

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“…Literature examples of O 2 – cluster formation via electric discharge and direct attachment of low-kinetic-energy electrons support the formation of the superoxide complex. − In the high m / z range (Figure b), a strong I – peak suggests that if any CH 3 OO is formed, complex formation by direct addition is also available. While previous work within the Wild Group has generated halide–molecule complexes readily in the gas phase by simple association, − the presence of a relatively intense O 2 – peak in the mass spectrum suggests that more complex dynamics may be present.…”

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confidence: 99%

Photoelectron Spectroscopy and High-Level Ab Initio Calculations of the Iodide–Methylperoxy Radical Complex

2022

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Anion photoelectron spectroscopy has been used to investigate the structure and dynamics of CH3OOI– van der Waals complexes. Peaks within the photoelectron spectrum are attributed to photodetachment to the perturbed 2P3/2 state of I···CH3OO (3.46 eV) and the two 2P states of bare iodine. A broad feature at 1.7–2.4 eV is attributed to detachment to the excited singlet states from two O2 –···CH3I complexes. This represents the first anion photoelectron spectroscopy of a halide-bound methylperoxy radical species. Complex structures have been optimized using MP2/aug-cc-pVQZ with single-point energies at W1w theory for ground-state complexes and NEVPT2 for photodetachment to excited O2. Interactions are dominated by electrostatics, with the anion species interacting with the methyl pocket of the solvating molecule, suggesting conversion via an S N2 mechanism, and excess energy leading to complex dissociation within the timescale of mass spectrometry. The calculated W1w Gibbs energies suggest that while an electron transfer (ET) pathway to conversion is available, it is comparatively unfavored.

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“…This is even less for the C s I − ⋅⋅⋅CH 3 CHO transition structure relative to the C 1 ground state. Therefore, it is entirely possible that the vibrationally averaged structure is of C s symmetry, similar to other systems explored by our group [9] …”

Section: Figurementioning

confidence: 57%

“…This solvent shift is largely dependent on the strength of the interaction between the halide anion and complexing neutral molecule [7] . Our group has recently combined anion photoelectron spectroscopy and CCSD(T) calculations to probe the electronic structure of systems involving halogen bonding, [8] as well as ion‐radical [9] and ion‐multipole [10] interactions.…”

Section: Figurementioning

confidence: 99%

“…While the stability of the anion complex ( D 0 ) has been established as an indicator of electron stabilisation ( E stab ) previously, [8–10] some effect on the neutral Franck‐Condon surface may be resulting in a lower E stab than expected for I − ⋅⋅⋅CH 3 CHO. Another way to delve further is to compare the predicted 2 P 3/2 detachment energies of I − ⋅⋅⋅CH 2 O from previous work and that of I − ⋅⋅⋅CH 3 CHO reported here, in order to ascertain if the theory is consistent with the experimental observation.…”

Section: Figurementioning

confidence: 99%

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

et al. 2021

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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.

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The bromide-bromomethyl radical dimer complex: Anion photoelectron spectroscopy and CCSD(T) calculations

Cited by 10 publications

References 43 publications

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

Photoelectron Spectroscopy and High-Level Ab Initio Calculations of the Iodide–Methylperoxy Radical Complex

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

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The bromide-bromomethyl radical dimer complex: Anion photoelectron spectroscopy and CCSD(T) calculations

Cited by 10 publications

References 43 publications

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

Spectroscopic Investigation of Chalcogen Bonding: Halide–Carbon Disulfide Complexes

Photoelectron Spectroscopy and High-Level Ab Initio Calculations of the Iodide–Methylperoxy Radical Complex

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

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