Kinetic energy release; Metastable; Photofragmentation; Ab initio calculations; ion-quadrupole/dipole complex; maximum entropy method; Phase space; Dimensionality; C5H5N; C6H6; C4H4+
Abstract :
[en] Kinetic energy release distributions (KERDs) for the benzene ion fragmenting into C4H4+ and C2H2 have been recorded by double-focussing mass spectrometry in the metastable energy window and by a retarding field experiment up to an energy of 5 eV above the fragmentation threshold. They are compared with those resulting from the HCN loss reaction from the pyridine ion. Both reactions display a similar variation of the kinetic energy release as a function of the internal energy: the average release is smaller than statistically expected, with a further restriction of the phase-space sampling for the C5H5N+ dissociation. Ab initio calculations of the potential-energy profile have been carried out. They reveal a complicated reaction mechanism, the last step of which consists in the dissociation of a weakly bound ion-quadrupole or ion-dipole complex. The KERDs have been analyzed by the maximum entropy method. The fraction of phase-space effectively sampled by the pair of fragments has been determined and is similar for both dissociations. Both reactions are constrained by the square root of the released kinetic energy, epsilon1/2. This indicates that in the latter stage of the dissociation process, the reaction coordinate is adiabatically decoupled from the bath of the bound degrees of freedom. For the C6H6+ fragmentation, the analysis of the experimental results strongly suggests that, just as for the symmetric interaction potential, the translational motion is confined to a two-dimensional subspace. This dimensionality reduction of the translational phase space is due to the fact that the Hamiltonian of both weakly bound complexes contains a cyclic coordinate.
Research center :
Laboratoire de Dynamique Moléculaire
Disciplines :
Chemistry
Author, co-author :
Gridelet, E.
Locht, Robert ; Université de Liège - ULiège > Département de Chimie (Faculté des sciences) > Laboratoire de Dynamique Moléculaire (Sciences)
Lorquet, Andrée ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Lorquet, Jean-Claude ; Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences)
Leyh, Bernard ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Language :
English
Title :
The Role of Long-Range Forces in the Determination of Translational Kinetic Energy Release. Loss of C4H4+ from Benzene and Pyridine Cations.
Alternative titles :
[fr] Le role des forces à longues distances dans la determination de la libération d'énergie cinétique translationnelle. La formation de cations C4H4+ à partir du Benzène et de la Pyridine.
Publication date :
2008
Journal title :
Journal of Physical Chemistry. A
ISSN :
1089-5639
eISSN :
1520-5215
Publisher :
American Chemical Society, Washington DC, United States
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