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...
| Main Authors: | , |
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| Format: | Article |
| Language: | English |
| Published: |
American Institute of Physics
2016
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| Online Access: | http://eprints.nottingham.ac.uk/32079/ http://eprints.nottingham.ac.uk/32079/ http://eprints.nottingham.ac.uk/32079/ http://eprints.nottingham.ac.uk/32079/1/jcp-xes-final.pdf |
| Summary: | 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. |
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