An experimental guided-ion-beam and ab initio study of the ion-molecule gas-phase reactions between Li{sup +} ions and iso-C{sub 3}H{sub 7}Cl in their ground electronic state

Journal Article · Tue Jul 14 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3168332· OSTI ID:21559864

Lucas, J M; Andres, J de; Sogas, J; Alberti, M; Aguilar, A ^[1]; Bofill, J M ^[2]; Bassi, D; Ascenzi, D; Tosi, P ^[3]

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1. Departament de Quimica Fisica, Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain)
2. Departament de Quimica Organica, Institut de Quimica Teorica i Computacional (IQTCUB), Universitat de Barcelona, Marti i Franques, 1, 08028 Barcelona (Spain)
3. Dipartimento di Fisica, Universita degli Studi di Trento, 38050 Povo-Trento (Italy)

Reactive collisions between Li{sup +} ions and i-C{sub 3}H{sub 7}Cl molecules have been studied in the 0.20-12.00 eV center-of-mass energy range using an octopole radio frequency guided-ion beam apparatus recently developed in our laboratory. At low collision energies, dehydrohalogenation reactions giving rise to Li(C{sub 3}H{sub 6}){sup +} and Li(HCl){sup +} are the main reaction channels, while at higher ones C{sub 3}H{sub 7}{sup +} and C{sub 2}H{sub 3}{sup +} become dominant, all their reactive cross sections having been measured as a function of the collision energy. To obtain information about the potential energy surfaces (PESs) on which the reactive processes take place, ab initio calculations at the MP2 level have been performed. For dehydrohalogenations, the reactive ground singlet PES shows ion-molecule adduct formation in both the reactant and product sides of the surface. Following the minimum energy path connecting both minima, an unstable intermediate and the corresponding barriers, both lying below the reactant's energy, have been characterized. The entrance channel ion-molecule adduct is also involved in the formation of C{sub 3}H{sub 7}{sup +}, which then generates C{sub 2}H{sub 3}{sup +} via an CH{sub 4} unimolecular elimination. A qualitative interpretation of the experimental results based on ab initio calculations is also included.

• OSTI ID: 21559864
• Journal Information: Journal of Chemical Physics, Vol. 131, Issue 2; Other Information: DOI: 10.1063/1.3168332; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ADDUCTS
CATIONS
CENTER-OF-MASS SYSTEM
CROSS SECTIONS
EV RANGE
GROUND STATES
HYDROCHLORIC ACID
ION BEAMS
ION-MOLECULE COLLISIONS
LITHIUM
LITHIUM IONS
METHANE
MOLECULES
PERTURBATION THEORY
POTENTIAL ENERGY
PROPYLENE
RADIOWAVE RADIATION
SURFACES
ALKALI METALS
ALKANES
ALKENES
BEAMS
CHARGED PARTICLES
CHLORINE COMPOUNDS
COLLISIONS
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY
ENERGY LEVELS
ENERGY RANGE
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN COMPOUNDS
INORGANIC ACIDS
INORGANIC COMPOUNDS
ION COLLISIONS
IONS
METALS
MOLECULE COLLISIONS
ORGANIC COMPOUNDS
RADIATIONS