The Role of Long-Range Forces in the Determination of Translational Kinetic Energy Release. Loss of C4H4 + from the Benzene and Pyridine Cations

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 112; no. 41; pp. 10086 - 10095
• Main Authors: Gridelet, E, Locht, R, Lorquet, A. J, Lorquet, J. C, Leyh, B
• Format: Journal Article Web Resource
• Language: English
• Published: United States American Chemical Society 16.10.2008
• Subjects: A: Dynamics, Clusters, Excited States; Ab initio calculations; C4H4; C5H5N; C6H6; Chemistry; Chimie; Dimensionality; ion-quadrupole/dipole complex; Kinetic energy release; maximum entropy method; Metastable; Phase space; Photofragmentation; Physical, chemical, mathematical & earth Sciences; Physique, chimie, mathématiques & sciences de la terre
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/jp8033424

Kinetic energy release distributions (KERDs) for the benzene ion fragmenting into C4H4 + and C2H2 have been recorded by double-focusing 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 translational energy, ε1/2. 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 a spherically symmetric interaction potential, the translational motion is confined to a plane. For the dissociation of the pyridine ion, the main dynamical constraint is also a restriction 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.