Closing the Shell: Gas-Phase Solvation of Halides by 1,3-Butadiene.

Gas-phase solvation of halides by 1,3-butadiene has been studied via a combination of photoelectron spectroscopy and density functional theory. Photoelectron spectra for X ⋯(C H ) (X=Cl, Br, I where n=1-3, 1-3 and 1-7 respectively) are presented. For all complexes, the calculated structures indicate that butadiene is bound in a bidentate fashion through hydrogen-bonding, with the chloride complex showing the greatest degree of stabilisation of the internal C-C rotation of cis-butadiene.

Hydrogen Bonding versus Halogen Bonding: Spectroscopic Investigation of Gas-Phase Complexes Involving Bromide and Chloromethanes.

Hydrogen bonding and halogen bonding are important non-covalent interactions that are known to occur in large molecular systems, such as in proteins and crystal structures. Although these interactions are important on a large scale, studying hydrogen and halogen bonding in small, gas-phase chemical species allows for the binding strengths to be determined and compared at a fundamental level. In this study, anion photoelectron spectra are presented for the gas-phase complexes involving bromide and the four chloromethanes, CH Cl, CH Cl , CHCl , and CCl .

Halide-propene complexes: validated DSD-PBEP86-D3BJ calculations and photoelectron spectroscopy.

Anion photoelectron spectroscopy has been used to determine the electron binding energies of the X⋯CH (X = Cl, Br, I) complexes. To complement the experimental spectra the DSD-PBEP86-D3BJ functional has been employed, following comparison with previously calculated halide/halogen-molecule van der Waals complexes. To validate the functional, comparison between the complex geometries and vertical detachment energies with both experimental and CCSD(T)/CBS data for a suite of halide-molecule complexes is also made.

A tale of two conformers: spectroscopic evidence for halide catalysed formic acid isomerisation.

Halide-formic acid complexes have been studied utilising a combined experimental and theoretical approach. Formic acid exists as two conformers, distinguished by the relative rotation about the C-OH bond. Computational investigation of the formic acid isomerisation reaction between the two conformers has revealed the ability of halide anions to catalyse the formation of, and preferentially stabilise, the higher energy conformer.

Spectroscopic Study of the Br +CH I→I +CH Br S 2 Reaction.

Mass spectrometry and anion photoelectron spectroscopy have been used to study the gas-phase reaction involving and . The anion photoelectron spectra associated with the reaction intermediates of this reaction are presented. High-level CCSD(T) calculations have been utilised to investigate the reaction intermediates that may form as a result of the reaction along various different reaction pathways, including back-side attack and front-side attack.

Towards an Understanding of Halide Interactions with the Carbonyl-Containing Molecule CH CHO.

The anion photoelectron spectra of Cl ⋅⋅⋅CD CDO, Cl ⋅⋅⋅(CD CDO) , Br ⋅⋅⋅CH CHO, and I ⋅⋅⋅CH CHO are presented with electron stabilisation energies of 0.55, 0.93, 0.

Spectroscopic Investigation of Chalcogen Bonding: Halide-Carbon Disulfide Complexes.

A combined experimental and theoretical approach has been used to study intermolecular chalcogen bonding. Specifically, the chalcogen bonding occurring between halide anions and CS 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.

Photoelectron Spectroscopy and Structures of X ⋅⋅⋅CH O (X=F, Cl, Br, I) Complexes.

A combined experimental and theoretical approach has been used to investigate X ⋅⋅⋅CH O (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 ⋅⋅⋅CH O, Br ⋅⋅⋅CH O, and I ⋅⋅⋅CH O species. Additionally, high-level CCSD(T) calculations found a C minimum for these three anion complexes, with predicted electron detachment energies in excellent agreement with the experimental photoelectron spectra.

The Structure of CCl in the Gas Phase.

The first experimental evidence of the structure of the CCl gas-phase anion complex is presented in conjunction with results from high-level theoretical calculations. The photoelectron spectrum of the system shows a single peak with a maximum at 4.22 eV.