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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 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 Thumbnail


Authors

Ian P.E. Roper

Nicholas A. Besley



Abstract

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.

Citation

Roper, I. P., & Besley, N. A. (in press). 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, Article 114104. https://doi.org/10.1063/1.4943862

Journal Article Type Article
Acceptance Date Mar 1, 2016
Online Publication Date Mar 16, 2016
Deposit Date Mar 2, 2016
Publicly Available Date Mar 16, 2016
Journal Journal of Chemical Physics
Print ISSN 0021-9606
Electronic ISSN 1089-7690
Publisher American Institute of Physics
Peer Reviewed Peer Reviewed
Volume 144
Article Number 114104
DOI https://doi.org/10.1063/1.4943862
Keywords TDDFT, X-ray emission spectroscopy
Public URL https://nottingham-repository.worktribe.com/output/780169
Publisher URL http://scitation.aip.org/content/aip/journal/jcp/144/11/10.1063/1.4943862
Related Public URLs http://scitation.aip.org/content/aip/journal/jcp
Additional Information Copyright 2016 AIP Publishing. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing.
The following article has been submitted to/accepted by Journal of Chemical Physics. After it is published, it will be found at http://scitation.aip.org/content/aip/journal/jcp

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