Functional and basis set dependence of K-edge shake-up spectra of molecules.

A straightforward approach for computing the K-edge shake-up spectra of molecules based on equivalent core-hole linear response theory at both Hartree–Fock and density functional theory levels is proposed. Benchmark calculations have been performed to explore its sensitivity to different types of functionals and basis sets for the carbon 1s shake-up spectra of benzene and metal-free phthalocyanine (H2Pc). A very good agreement with previous theoretical and experimental works for the benzene molecule has been obtained for all the functionals and basis sets tested. Electron correlation is found to be essential for a good description of the H2Pc system, whose experimental C 1s shake-up spectrum is best reproduced by the hybrid density functional. [ABSTRACT FROM AUTHOR]