dorsal/arxiv
View SchemaThe structure of the hydrated electron. Part 2. A mixed quantum classical molecular dynamics - embedded cluster density functional theory: single-excitation configuration interaction study
| Authors | Ilya A. Shkrob, William J. Glover, Ross E. Larsen, Benjamin J. Schwartz |
|---|---|
| Categories | |
| ArXiv ID | physics/0611176 |
| URL | https://arxiv.org/abs/physics/0611176 |
| DOI | 10.1021/jp0682816 |
Abstract
Adiabatic mixed quantum/classical molecular dynamics simulations were used to generate snapshots of the hydrated electron (e-) in liquid water at 300 K. Water cluster anions that include two complete solvation shells centered on the e- were extracted from these simulations and embedded in a matrix of fractional point charges designed to represent the rest of the solvent. Density functional theory and single-excitation configuration interaction methods were then applied to these embedded clusters. The salient feature of these hybrid calculations is significant transfer (ca. 0.18) of the excess electron's charge density into the O 2p orbitals in OH groups forming the solvation cavity. We used the results of these calculations to examine the structure of the molecular orbitals, the density of states, the absorption spectra in the visible and ultraviolet, the hyperfine coupling (hfc) tensors, and the IR and Raman spectra of the e-. The calculated hfc tensors were used to compute the EPR and ESEEM spectra for the e- that compared favorably to the experimental spectra of trapped e- in alkaline ice. The calculated vibrational spectra of the e- are consistent with the red-shifted bending and stretching frequencies observed in resonance Raman experiments. The model also accounts for the VIS and 190-nm absorption bands of the e-. Thus, our study suggests that to explain several important experimentally observed properties of the e-, many-electron effects must be accounted for.
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"abstract": "Adiabatic mixed quantum/classical molecular dynamics simulations were used to\ngenerate snapshots of the hydrated electron (e-) in liquid water at 300 K.\nWater cluster anions that include two complete solvation shells centered on the\ne- were extracted from these simulations and embedded in a matrix of fractional\npoint charges designed to represent the rest of the solvent. Density functional\ntheory and single-excitation configuration interaction methods were then\napplied to these embedded clusters. The salient feature of these hybrid\ncalculations is significant transfer (ca. 0.18) of the excess electron\u0027s charge\ndensity into the O 2p orbitals in OH groups forming the solvation cavity. We\nused the results of these calculations to examine the structure of the\nmolecular orbitals, the density of states, the absorption spectra in the\nvisible and ultraviolet, the hyperfine coupling (hfc) tensors, and the IR and\nRaman spectra of the e-. The calculated hfc tensors were used to compute the\nEPR and ESEEM spectra for the e- that compared favorably to the experimental\nspectra of trapped e- in alkaline ice. The calculated vibrational spectra of\nthe e- are consistent with the red-shifted bending and stretching frequencies\nobserved in resonance Raman experiments. The model also accounts for the VIS\nand 190-nm absorption bands of the e-. Thus, our study suggests that to explain\nseveral important experimentally observed properties of the e-, many-electron\neffects must be accounted for.",
"arxiv_id": "physics/0611176",
"authors": [
"Ilya A. Shkrob",
"William J. Glover",
"Ross E. Larsen",
"Benjamin J. Schwartz"
],
"categories": [
"physics.data-an"
],
"doi": "10.1021/jp0682816",
"title": "The structure of the hydrated electron. Part 2. A mixed quantum classical molecular dynamics - embedded cluster density functional theory: single-excitation configuration interaction study",
"url": "https://arxiv.org/abs/physics/0611176"
},
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