dorsal/arxiv
View SchemaApplication of time-dependent density-functional theory to electron-ion couplng in ethylene
| Authors | G. F. Bertsch, J. Giansiracusa, K. Yabana |
|---|---|
| Categories | |
| ArXiv ID | physics/0210043 |
| URL | https://arxiv.org/abs/physics/0210043 |
| Journal | Israel Journal of Chemistry 42 151 (2002) |
Abstract
To examine the applicability of the time-dependent density-functional theory (TDDFT) for treating the electron-nucleus coupling in excited states, we calculate the strength distribution associated with the pi-pi* transition in ethylene. The observed optical transition strength at 7-8.5 eV region shows a complex structure arising from coupling to C-C stretch motion, to torsional motion, and to Rydberg excitations. The mean energy of the observed peak is reproduced to about 0.2 eV accuracy by the TDDFT in the local density approximation (LDA). The reflection approximation is used to calculate the peak broadening. Roughly half of the broadening can be attributed to the fluctuation in the C-C coordinate. The asymmetry in the line shape is also qualitatively reproduced by the C-C coordinate fluctuation. We find, in agreement with other theoretical studies, that the torsional motion is responsible for the progression of weak transition strength extending from the peak down to about 6 eV. The LDA reproduces the strength in this region to about factor of 3. We conclude that the TDDFT is rather promising for calculating the electron nucleus coupling at short times.
{
"annotation_id": "283863de-dd7a-4235-be49-50b2338772ec",
"date_created": "2026-03-02T18:00:39.896000Z",
"date_modified": "2026-03-02T18:00:39.896000Z",
"file_hash": "8b7ab40e5a03653219f45a2fc3fce88ce921f2201b86be00548c45e463a40e72",
"private": false,
"record": {
"abstract": "To examine the applicability of the time-dependent density-functional theory\n(TDDFT) for treating the electron-nucleus coupling in excited states, we\ncalculate the strength distribution associated with the pi-pi* transition in\nethylene. The observed optical transition strength at 7-8.5 eV region shows a\ncomplex structure arising from coupling to C-C stretch motion, to torsional\nmotion, and to Rydberg excitations. The mean energy of the observed peak is\nreproduced to about 0.2 eV accuracy by the TDDFT in the local density\napproximation (LDA). The reflection approximation is used to calculate the peak\nbroadening. Roughly half of the broadening can be attributed to the fluctuation\nin the C-C coordinate. The asymmetry in the line shape is also qualitatively\nreproduced by the C-C coordinate fluctuation. We find, in agreement with other\ntheoretical studies, that the torsional motion is responsible for the\nprogression of weak transition strength extending from the peak down to about 6\neV. The LDA reproduces the strength in this region to about factor of 3. We\nconclude that the TDDFT is rather promising for calculating the electron\nnucleus coupling at short times.",
"arxiv_id": "physics/0210043",
"authors": [
"G. F. Bertsch",
"J. Giansiracusa",
"K. Yabana"
],
"categories": [
"physics.chem-ph"
],
"journal_ref": "Israel Journal of Chemistry 42 151 (2002)",
"title": "Application of time-dependent density-functional theory to electron-ion couplng in ethylene",
"url": "https://arxiv.org/abs/physics/0210043"
},
"schema_id": "dorsal/arxiv",
"source": {
"execution_id": "b263c4a7-415b-4596-b0b0-a74dbaab87e7",
"id": "arXiv Dataset IDs",
"type": "Model",
"variant": "snapshot-2026-03-01",
"version": "0.1.0"
},
"user_id": 1000002
}