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 approximation 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 considering 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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21 March 2016
Research Article|
March 16 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
Ian P. E. Roper;
Ian P. E. Roper
School of Chemistry,
University of Nottingham
, University Park, Nottingham NG7 2RD, United Kingdom
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Nicholas A. Besley
Nicholas A. Besley
a)
School of Chemistry,
University of Nottingham
, University Park, Nottingham NG7 2RD, United Kingdom
Search for other works by this author on:
School of Chemistry,
University of Nottingham
, University Park, Nottingham NG7 2RD, United Kingdom
J. Chem. Phys. 144, 114104 (2016)
Article history
Received:
November 24 2015
Accepted:
March 01 2016
Citation
Ian P. E. Roper, Nicholas A. Besley; 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. J. Chem. Phys. 21 March 2016; 144 (11): 114104. https://doi.org/10.1063/1.4943862
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