The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes
The simulation of X-ray emission spectra of transition metal complexes with time- dependent density functional theory (TDDFT) is investigated. X-ray emission spectra can be computed within TDDFT in conjunction with the Tamm-Dancoff approximation by using a reference determinant with a vacancy in the...
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| Format: | Article |
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American Institute of Physics
2016
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| Online Access: | https://eprints.nottingham.ac.uk/32079/ |
| _version_ | 1848794330629668864 |
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| author | Roper, Ian P.E. Besley, Nicholas A. |
| author_facet | Roper, Ian P.E. Besley, Nicholas A. |
| author_sort | Roper, Ian P.E. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The simulation of X-ray emission spectra of transition metal complexes with time- dependent density functional theory (TDDFT) is investigated. X-ray emission spectra can be computed within TDDFT in conjunction with the Tamm-Dancoff approximation by using a reference determinant with a vacancy in the relevant core orbital, and these calculations can be performed using the frozen orbital approxi- mation or with the relaxation of the orbitals of the intermediate core-ionised state included. Both standard exchange-correlation functionals and functionals specifically designed for X-ray emission spectroscopy are studied, and it is shown that the computed spectral band profiles are sensitive to the exchange-correlation functional used. The computed intensities of the spectral bands can be rationalised by consid- ering the metal p orbital character of the valence molecular orbitals. To compute X-ray emission spectra with the correct energy scale allowing a direct comparison with experiment requires the relaxation of the core-ionised state to be included and the use of specifically designed functionals with increased amounts of Hartree-Fock exchange in conjunction with high quality basis sets. A range-corrected functional with increased Hartree-Fock exchange in the short range provides transition energies close to experiment and spectral band profiles that have a similar accuracy to those from standard functionals. |
| first_indexed | 2025-11-14T19:14:29Z |
| format | Article |
| id | nottingham-32079 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:14:29Z |
| publishDate | 2016 |
| publisher | American Institute of Physics |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-320792020-05-04T17:41:43Z https://eprints.nottingham.ac.uk/32079/ The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes Roper, Ian P.E. Besley, Nicholas A. The simulation of X-ray emission spectra of transition metal complexes with time- dependent density functional theory (TDDFT) is investigated. X-ray emission spectra can be computed within TDDFT in conjunction with the Tamm-Dancoff approximation by using a reference determinant with a vacancy in the relevant core orbital, and these calculations can be performed using the frozen orbital approxi- mation or with the relaxation of the orbitals of the intermediate core-ionised state included. Both standard exchange-correlation functionals and functionals specifically designed for X-ray emission spectroscopy are studied, and it is shown that the computed spectral band profiles are sensitive to the exchange-correlation functional used. The computed intensities of the spectral bands can be rationalised by consid- ering the metal p orbital character of the valence molecular orbitals. To compute X-ray emission spectra with the correct energy scale allowing a direct comparison with experiment requires the relaxation of the core-ionised state to be included and the use of specifically designed functionals with increased amounts of Hartree-Fock exchange in conjunction with high quality basis sets. A range-corrected functional with increased Hartree-Fock exchange in the short range provides transition energies close to experiment and spectral band profiles that have a similar accuracy to those from standard functionals. American Institute of Physics 2016-03-16 Article PeerReviewed Roper, Ian P.E. and Besley, Nicholas A. (2016) The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes. Journal of Chemical Physics, 144 . 114104/1-114104/9. ISSN 1089-7690 TDDFT X-ray emission spectroscopy http://scitation.aip.org/content/aip/journal/jcp/144/11/10.1063/1.4943862 doi:10.1063/1.4943862 doi:10.1063/1.4943862 |
| spellingShingle | TDDFT X-ray emission spectroscopy Roper, Ian P.E. Besley, Nicholas A. The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes |
| title | The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes |
| title_full | The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes |
| title_fullStr | The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes |
| title_full_unstemmed | The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes |
| title_short | The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm-Dancoff approximation of the X-ray emission spectroscopy of transition metal complexes |
| title_sort | effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the tamm-dancoff approximation of the x-ray emission spectroscopy of transition metal complexes |
| topic | TDDFT X-ray emission spectroscopy |
| url | https://eprints.nottingham.ac.uk/32079/ https://eprints.nottingham.ac.uk/32079/ https://eprints.nottingham.ac.uk/32079/ |