Survey of the Reactivity of O2(a 1Δg) with Negative Ions
| Autor: | Veronica M. Bierbaum, A. A. Viggiano, Nicole Eyet, Anthony Midey |
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| Rok vydání: | 2009 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 114:1270-1276 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp904235m |
| Popis: | The reactivity of O(2)(a (1)Delta(g)) was studied with a series of anions, including (-)CH(2)CN, (-)CH(2)NO(2), (-)CH(2)C(O)H, CH(3)C(O)CH(2)(-), C(2)H(5)O(-), (CH(3))(2)CHO(-), CF(3)CH(2)O(-), CF(3)(-), HC(2)(-), HCCO(-), HC(O)O(-), CH(3)C(O)O(-), CH(3)OC(O)CH(2)(-), and HS(-). Reaction rate constants and product ion branching ratios were measured. All of the carbanions react through a common pathway to produce their major products. O(2)(a) adds across a bond at the site of the negative charge, resulting in the cleavage of this bond and the O=O bond. Oxyanions react through a hydride transfer to produce their major products. Proton transfer within these product ion-dipole complexes can occur, where the final branching ratios reflect the basicity of the resulting anions. Several of these anions (CF(3)(-), HC(2)(-), CH(3)OC(O)CH(2)(-)) were also found to undergo several sequential reactions within a single encounter. These three basic types of mechanisms are supported by calculations; a potential energy diagram for each type of reaction has been calculated. Additionally, six of these reactions had been qualitatively studied before; our results are in agreement with previous data. |
| Databáze: | OpenAIRE |
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