Ground and excited state dissociation dynamics of ionized 1,1-difluoroethene.
The kinetic energy release distributions (KERDs) for the fluorine atom loss from the 1,1-difluoroethene cation have been recorded with two spectrometers in two different energy ranges. A first experiment uses dissociative photoionization with the He(I) and Ne(I) resonance lines, providing the ions with a broad internal energy range, up to 7 eV above the dissociation threshold. The second experiment samples the metastable range, and the average ion internal energy is limited to about 0.2 eV above the threshold. In both energy domains, KERDs are found to be bimodal. Each component has been analyzed by the maximum entropy method. The narrow, low kinetic energy components display for both experiments the characteristics of a statistical, simple bond cleavage reaction: constraint equal to the square root of the fragment kinetic energy and ergodicity index higher than 90%. Furthermore, this component is satisfactorily accounted for in the metastable time scale by the orbiting transition state theory. Potential energy surfaces corresponding to the five lowest electronic states of the dissociating 1,1-C2H2F2+ ion have been investigated by ab initio calculations at various levels. The equilibrium geometry of these states, their dissociation energies, and their vibrational wavenumbers have been calculated, and a few conical intersections between these surfaces have been identified. It comes out that the ionic ground state X2B1 is adiabatically correlated with the lowest dissociation asymptote. Its potential energy curve increases in a monotonic way along the reaction coordinate, giving rise to the narrow KERD component. Two states embedded in the third photoelectron band (B2A1 at 15.95 eV and C2B2 at 16.17 eV) also correlate with the lowest asymptote at 14.24 eV. We suggest that their repulsive behavior along the reaction coordinate be responsible for the KERD high kinetic energy contribution.
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Department of Chemistry, Molecular Dynamics Laboratory, Building B6c, and Centre for Protein Engineering, Building B6a, University of Liège, B-4000 SART-TILMAN, Belgium.
Dehareng
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Locht
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Lorquet
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Lorquet
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JC
Leyh
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D004355:Drug Stability; D019277:Entropy; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D007477:Ions; D007700:Kinetics; D010777:Photochemistry; D013816:Thermodynamics
D006845:Hydrocarbons, Fluorinated; D007477:Ions; C059268:1,1-difluoroethane