title: Dehydrohalogenation and Dehydration Reactions of i-C3H7Br and i-C3H7OH by Sodium Ions Studied by Guided Ion Beam Techniques and Quantum Chemical Methods.
abstract: Dehydrohalogenation and dehydration reactions of gas-phase i-C3H7Br and i-C3H7OH molecules induced by collision with Na(+), all participants being in their electronic ground state, were studied experimentally in our laboratory using a radiofrequency-guided ion beam apparatus and covering the 0.10-10.00 eV center of mass (CM) energy range. In Na(+) + i-C3H7Br collisions the formation of [C3H6-Na](+) and [HBr-Na](+) by dehydrohalogenation was observed and quantified, as well as that of the ion-molecule adduct [Na-i-C3H7Br](+) together with its decomposition products C3H7(+) and NaBr. In Na(+) + i-C3H7OH collisions the dehydration product [H2O-Na](+) was also found, while [C3H6-Na](+) was hardly detected. Moreover, the [Na-i-C3H7OH](+) adduct formation as well as its decomposition into C3H7(+) and NaOH were also quantified. For all these processes, absolute reaction cross sections were measured as a function of the CM collision energy. From measured excitation functions, rate constants for the formation of [C3H6-Na](+), [HBr-Na](+), and [H2O-Na](+) at 303 K were obtained. Complementing the experiments, exhaustive ab initio structure calculations at the MP2 level of theory were performed, giving information on the most relevant features of the potential energy surfaces (PESs) where the dehydrohalogenation, dehydration, and decomposition reactions take place adiabatically for both collision systems. On these PESs different stationary points associated with potential energy minima and transition state barriers were characterized, and their connectivity was ensured using the intrinsic-reaction-coordinate method. The main topology features of the ab initio calculated PESs allowed a qualitative interpretation of the experimental data also exposing the role of the sodium ion as a catalyst in elimination reactions.
authors.affiliation: Departament de Química Física and ‡Departament de Química Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona , Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: E
authors.initials: E
authors.lastname: López
authors.affiliation: Departament de Química Física and ‡Departament de Química Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona , Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: J M
authors.initials: JM
authors.lastname: Lucas
authors.affiliation: Departament de Química Física and ‡Departament de Química Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona , Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: J
authors.initials: J
authors.lastname: de Andrés
authors.affiliation: Departament de Química Física and ‡Departament de Química Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona , Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: M
authors.initials: M
authors.lastname: Albertí
authors.affiliation: Departament de Química Física and ‡Departament de Química Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona , Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: J M
authors.initials: JM
authors.lastname: Bofill
authors.affiliation: Departament de Química Física and ‡Departament de Química Orgànica, Institut de Química Teòrica i Computacional, Universitat de Barcelona , Martí i Franquès, 1, 08028 Barcelona, Spain.
authors.forename: A
authors.initials: A
authors.lastname: Aguilar