dorsal/arxiv
View SchemaElectron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution
| Authors | Ilya A. Shkrob, Myran C. Sauer, Jr. |
|---|---|
| Categories | |
| ArXiv ID | physics/0501086 |
| URL | https://arxiv.org/abs/physics/0501086 |
| DOI | 10.1021/jp050564v |
Abstract
Monomers and small clusters of such molecules can reversibly trap conduction band electrons in dilute alkane solutions. The dynamics and energetics of this trapping have been studied using pulse radiolysis - transient absorption spectroscopy and time-resolved photoconductivity. Binding energies, thermal detrapping rates, and absorption spectra of excess electrons attached to monomer and multimer solute traps are obtained and possible structures for these species are discussed. "Dipole coagulation" (stepwise growth of the solute cluster around the cavity electron) predicted by Mozumder in 1972 is observed. Acetonitrile monomer is shown to solvate the electron by its methyl group, just like the alkane solvent does. The electron is dipole-bound to the CN group; the latter points away from the cavity. The resulting negatively charged species has a binding energy of 0.4 eV and absorbs in the infrared. Molecules of straight-chain aliphatic alcohols solvate the excess electron by their OH groups; at equilibrium, the predominant electron trap is a trimer or a tetramer; the binding energy of this solute trap is ca. 0.8 eV. Trapping by smaller clusters is opposed by the entropy which drives the equilibrium towards the electron in a solvent trap. For alcohol monomers, the trapping does not occur; a slow proton transfer reaction occurs instead. For acetonitrile monomer, the trapping is favored energetically but the thermal detachment is rapid (ca. 1 ns).
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"abstract": "Monomers and small clusters of such molecules can reversibly trap conduction\nband electrons in dilute alkane solutions. The dynamics and energetics of this\ntrapping have been studied using pulse radiolysis - transient absorption\nspectroscopy and time-resolved photoconductivity. Binding energies, thermal\ndetrapping rates, and absorption spectra of excess electrons attached to\nmonomer and multimer solute traps are obtained and possible structures for\nthese species are discussed. \"Dipole coagulation\" (stepwise growth of the\nsolute cluster around the cavity electron) predicted by Mozumder in 1972 is\nobserved. Acetonitrile monomer is shown to solvate the electron by its methyl\ngroup, just like the alkane solvent does. The electron is dipole-bound to the\nCN group; the latter points away from the cavity. The resulting negatively\ncharged species has a binding energy of 0.4 eV and absorbs in the infrared.\nMolecules of straight-chain aliphatic alcohols solvate the excess electron by\ntheir OH groups; at equilibrium, the predominant electron trap is a trimer or a\ntetramer; the binding energy of this solute trap is ca. 0.8 eV. Trapping by\nsmaller clusters is opposed by the entropy which drives the equilibrium towards\nthe electron in a solvent trap. For alcohol monomers, the trapping does not\noccur; a slow proton transfer reaction occurs instead. For acetonitrile\nmonomer, the trapping is favored energetically but the thermal detachment is\nrapid (ca. 1 ns).",
"arxiv_id": "physics/0501086",
"authors": [
"Ilya A. Shkrob",
"Myran C. Sauer, Jr."
],
"categories": [
"physics.chem-ph"
],
"doi": "10.1021/jp050564v",
"title": "Electron Trapping by Polar Molecules in Alkane Liquids: Cluster Chemistry in Dilute Solution",
"url": "https://arxiv.org/abs/physics/0501086"
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