The charge transfer excited state of the I−⋅CH3ISN2 reaction intermediate: Photoinduced intracluster dissociative attachment
| Autor: | Christopher G. Bailey, Donna M. Cyr, David Serxner, Mark A. Johnson, M. Georgina Scarton |
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| Rok vydání: | 1994 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 101:10507-10520 |
| ISSN: | 1089-7690 0021-9606 |
| Popis: | We describe the reaction dynamics which occur upon excitation of the I−⋅CH3I ion–molecule complex to the first optically allowed excited electronic state. Photoelectron spectroscopy of I−⋅CH3I confirms the identification of the species as essentially charge localized, where the observed vibrational fine structure is found to be consistent with small distortions of the CH3I neutral upon complexation to form a stable intermediate in the SN2 identity reaction. A narrow photofragmentation band lies just below the vertical electron detachment energy and is assigned to the I−⋅CH3I→I...[CH3I]− charge transfer excited state. The recoil energy imparted to the I− fragment is only about 10% of the available energy, indicating that most of the energy is lost to the methyl group as expected for an impulsive dissociation. The I− photoproduct is preferentially ejected along the electric vector of the laser with an anisotropy parameter β of +0.5±0.2. This requires that photoabsorption occurs to a repulsive state which di... |
| Databáze: | OpenAIRE |
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