Calculating excited state properties using Kohn-Sham density functional theory
The accuracy of excited states calculated with Kohn-Sham density functional theory using the maximum overlap method has been assessed for the calculation of adiabatic excitation energies, excited state structures, and excited state harmonic and anharmonic vibrational frequencies for open-shell singl...
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| Format: | Article |
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American Institute of Physics
2013
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| Online Access: | https://eprints.nottingham.ac.uk/29965/ |
| _version_ | 1848793892739088384 |
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| author | Hanson-Heine, Magnus W.D. George, Michael W. Besley, Nicholas A. |
| author_facet | Hanson-Heine, Magnus W.D. George, Michael W. Besley, Nicholas A. |
| author_sort | Hanson-Heine, Magnus W.D. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The accuracy of excited states calculated with Kohn-Sham density functional theory using the maximum overlap method has been assessed for the calculation of adiabatic excitation energies, excited state structures, and excited state harmonic and anharmonic vibrational frequencies for open-shell singlet excited states. The computed Kohn-Sham adiabatic excitation energies are improved significantly by post self-consistent-field spin-purification, but remain too low compared with experiment with a larger error than time-dependent density functional theory. Excited state structures and vibrational frequencies are also improved by spin-purification. The structures show a comparable accuracy to time-dependent density functional theory, while the harmonic vibrational frequencies are found to be more accurate for the majority of vibrational modes. The computed harmonic vibrational frequencies are also further improved by perturbative anharmonic corrections, suggesting a good description of the potential energy surface. Overall, excited state Kohn-Sham density functional theory is shown to provide an efficient method for the calculation of excited state structures and vibrational frequencies in open-shell singlet systems, and provides a promising technique that can be applied to study large systems. |
| first_indexed | 2025-11-14T19:07:31Z |
| format | Article |
| id | nottingham-29965 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:07:31Z |
| publishDate | 2013 |
| publisher | American Institute of Physics |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-299652020-05-04T16:35:47Z https://eprints.nottingham.ac.uk/29965/ Calculating excited state properties using Kohn-Sham density functional theory Hanson-Heine, Magnus W.D. George, Michael W. Besley, Nicholas A. The accuracy of excited states calculated with Kohn-Sham density functional theory using the maximum overlap method has been assessed for the calculation of adiabatic excitation energies, excited state structures, and excited state harmonic and anharmonic vibrational frequencies for open-shell singlet excited states. The computed Kohn-Sham adiabatic excitation energies are improved significantly by post self-consistent-field spin-purification, but remain too low compared with experiment with a larger error than time-dependent density functional theory. Excited state structures and vibrational frequencies are also improved by spin-purification. The structures show a comparable accuracy to time-dependent density functional theory, while the harmonic vibrational frequencies are found to be more accurate for the majority of vibrational modes. The computed harmonic vibrational frequencies are also further improved by perturbative anharmonic corrections, suggesting a good description of the potential energy surface. Overall, excited state Kohn-Sham density functional theory is shown to provide an efficient method for the calculation of excited state structures and vibrational frequencies in open-shell singlet systems, and provides a promising technique that can be applied to study large systems. American Institute of Physics 2013-02-14 Article PeerReviewed Hanson-Heine, Magnus W.D., George, Michael W. and Besley, Nicholas A. (2013) Calculating excited state properties using Kohn-Sham density functional theory. Journal of Chemical Physics, 138 (6). 064101/1-064101/8. ISSN 0021-9606 density functional theory http://scitation.aip.org/content/aip/journal/jcp/138/6/10.1063/1.4789813 doi:10.1063/1.4789813 doi:10.1063/1.4789813 |
| spellingShingle | density functional theory Hanson-Heine, Magnus W.D. George, Michael W. Besley, Nicholas A. Calculating excited state properties using Kohn-Sham density functional theory |
| title | Calculating excited state properties using Kohn-Sham density functional theory |
| title_full | Calculating excited state properties using Kohn-Sham density functional theory |
| title_fullStr | Calculating excited state properties using Kohn-Sham density functional theory |
| title_full_unstemmed | Calculating excited state properties using Kohn-Sham density functional theory |
| title_short | Calculating excited state properties using Kohn-Sham density functional theory |
| title_sort | calculating excited state properties using kohn-sham density functional theory |
| topic | density functional theory |
| url | https://eprints.nottingham.ac.uk/29965/ https://eprints.nottingham.ac.uk/29965/ https://eprints.nottingham.ac.uk/29965/ |