dorsal/arxiv
View SchemaThe Structure of Hydrated Electron. Part 1. Magnetic Resonance of Internally Trapping Water Anions: A Density Functional Theory Study
| Authors | I. A. Shkrob |
|---|---|
| Categories | |
| ArXiv ID | physics/0607228 |
| URL | https://arxiv.org/abs/physics/0607228 |
| DOI | 10.1021/jp068278m |
Abstract
Density functional theory (DFT) is used to rationalize magnetic parameters of hydrated electron trapped in alkaline glasses as observed using Electron Paramagnetic Resonance (EPR) and Electron Spin Echo Envelope Modulation (ESEEM) spectroscopies. To this end, model water cluster anions (n=4-8 and n=20,24) that localize the electron internally are examined. It is shown that EPR parameters of such water anions (such as hyperfine coupling tensors of H/D nuclei in the water molecules) are defined mainly by the cavity size and the coordination number of the electron; the water molecules in the second solvation shell play a relatively minor role. An idealized model of hydrated electron (that is usually attributed to L. Kevan) in which six hydroxyl groups arranged in an octahedral pattern point towards the common center is shown to provide the closest match to the experimental parameters, such as isotropic and anisotropic hyperfine coupling constants for the protons (estimated from ESEEM), the second moment of the EPR spectra, and the radius of gyration. The salient feature of these DFT models is the significant transfer (10-20%) of spin density into the frontal O 2p orbitals of water molecules. Spin bond polarization involving these oxygen orbitals accounts for small, negative hyperfine coupling constants for protons in hydroxyl groups that form the electron-trapping cavity. In Part 2, these results are generalized for more realistic geometries of core anions obtained using a dynamic one-electron mixed qunatum/classical molecular dynamics model.
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"abstract": "Density functional theory (DFT) is used to rationalize magnetic parameters of\nhydrated electron trapped in alkaline glasses as observed using Electron\nParamagnetic Resonance (EPR) and Electron Spin Echo Envelope Modulation (ESEEM)\nspectroscopies. To this end, model water cluster anions (n=4-8 and n=20,24)\nthat localize the electron internally are examined. It is shown that EPR\nparameters of such water anions (such as hyperfine coupling tensors of H/D\nnuclei in the water molecules) are defined mainly by the cavity size and the\ncoordination number of the electron; the water molecules in the second\nsolvation shell play a relatively minor role. An idealized model of hydrated\nelectron (that is usually attributed to L. Kevan) in which six hydroxyl groups\narranged in an octahedral pattern point towards the common center is shown to\nprovide the closest match to the experimental parameters, such as isotropic and\nanisotropic hyperfine coupling constants for the protons (estimated from\nESEEM), the second moment of the EPR spectra, and the radius of gyration. The\nsalient feature of these DFT models is the significant transfer (10-20%) of\nspin density into the frontal O 2p orbitals of water molecules. Spin bond\npolarization involving these oxygen orbitals accounts for small, negative\nhyperfine coupling constants for protons in hydroxyl groups that form the\nelectron-trapping cavity. In Part 2, these results are generalized for more\nrealistic geometries of core anions obtained using a dynamic one-electron mixed\nqunatum/classical molecular dynamics model.",
"arxiv_id": "physics/0607228",
"authors": [
"I. A. Shkrob"
],
"categories": [
"physics.gen-ph"
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"doi": "10.1021/jp068278m",
"title": "The Structure of Hydrated Electron. Part 1. Magnetic Resonance of Internally Trapping Water Anions: A Density Functional Theory Study",
"url": "https://arxiv.org/abs/physics/0607228"
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