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. 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

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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.

Item Type: Article
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
Keywords: TDDFT, X-ray emission spectroscopy
Schools/Departments: University of Nottingham UK Campus > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1063/1.4943862
Related URLs:
URLURL Type
http://scitation.aip.org/content/aip/journal/jcpUNSPECIFIED
Depositing User: Besley, Nick
Date Deposited: 02 Mar 2016 14:29
Last Modified: 14 Oct 2016 20:05
URI: http://eprints.nottingham.ac.uk/id/eprint/32079

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