Electron Localization in Solid Acetonitrile
| Autor: | Keiji Takeda, Ilya A. Shkrob, Ffrancon Williams |
|---|---|
| Rok vydání: | 2002 |
| Předmět: |
chemistry.chemical_classification
Chemistry Electron capture Electron localization function law.invention chemistry.chemical_compound Computational chemistry Chemical physics law Ab initio quantum chemistry methods Ionization Molecule Physics::Chemical Physics Physical and Theoretical Chemistry Acetonitrile Electron paramagnetic resonance Alkyl |
| Zdroj: | The Journal of Physical Chemistry A. 106:9132-9144 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp020759s |
| Popis: | Electron localization in the bulk condensed phases of acetonitrile differs drastically from the corresponding processes that take place in water and aliphatic alcohols. In particular, electron capture following the ionization of liquid and solid acetonitrile yields well-defined radical anions in place of the largely structureless solvated and trapped electrons characteristic of irradiated solutions and rigid glasses. This is remarkable given the many similarities that exist not only between the intrinsic properties of these individual solvent molecules, such as polarity, but also in their cooperative capacity to function as solvents. Here, with the aid of detailed experimental and computational studies, we examine on a fundamental level what gives rise to such a sharp contrast in the behavior of these alkyl cyanides as compared to water and alcohols. EPR and optical spectra, and ab initio calculations on the radical anions are used together with diffraction data for the crystal structures to demonstrate t... |
| Databáze: | OpenAIRE |
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