Photoionization and core resonances from range-separated density-functional theory: General formalism and example of the beryllium atom

We explore the merits of linear-response range-separated time-dependent density-functional theory (TDDFT) for the calculation of photoionization spectra. We consider two variants of range-separated TDDFT, namely, the time-dependent range-separated hybrid (TDRSH) scheme, which uses a global range-separation parameter, and the time-dependent locally range-separated hybrid (TDLRSH), which uses a local range-separation parameter, and compare with standard time-dependent local-density approximation (TDLDA) and time-dependent Hartree-Fock (TDHF). We show how to calculate photoionization spectra with these methods using the Sternheimer approach formulated in a non-orthogonal B-spline basis set with appropriate frequency-dependent boundary conditions. We illustrate these methods on the photoionization spectrum of the Be atom, focusing, in particular, on the core resonances. Both the TDRSH and TDLRSH photoionization spectra are found to constitute a large improvement over the TDLDA photoionization spectrum and a more modest improvement over the TDHF photoionization spectrum. Published under an exclusive license by AIP Publishing.

Automated summary

This article explores the merits of linear-response range-separated time-dependent density-functional theory (TDDFT) for calculating photoionization spectra. Two variants of range-separated TDDFT are considered and compared with standard methods. The article demonstrates the calculation of photoionization spectra using the Sternheimer approach and applies it to the photoionization spectrum of the Be atom. The results show significant improvement over traditional methods.