Electronic excitations from a linear-response range-separated hybrid scheme

Abstract

We study linear-response time-dependent density-functional theory (DFT) based on the single-determinant range-separated hybrid (RSH) scheme, i.e. combining a long-range Hartree-Fock exchange kernel with a short-range DFT exchange-correlation kernel, for calculating electronic excitation energies of molecular systems. It is an alternative to the long-range correction (LC) scheme which has a standard full-range DFT correlation kernel instead of only a short-range one. We discuss the local-density approximation (LDA) to the short-range exchange-correlation kernel, and assess the performance of the linear-response RSH scheme for singlet-singlet and singlet-triplet valence and Rydberg excitations in the N2, CO, H2CO, C2H4, and C6H6 molecules, and for the first charge-transfer excitation in the C2H4-C2F4 dimer. The introduction of long-range HF exchange corrects the underestimation of charge-transfer and high-lying Rydberg excitation energies obtained with standard (semi)local density-functional approximations, but also leads to underestimated excitation energies to low-lying spin-triplet valence states which can be cured by the Tamm-Dancoff approximation. This work thus suggests that the present linear-response RSH scheme is a reasonable starting approximation for describing electronic excitation energies, even before adding an explicit treatment of long-range correlation.

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Cited by in corpus (13)

• A general range-separated double-hybrid density-functional theory
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• A reduced basis approach for calculation of the Bethe-Salpeter excitation energies using low-rank tensor factorizations
• Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients
• Four-component relativistic range-separated density-functional theory: Short-range exchange local-density approximation
• Excitation energies along a range-separated adiabatic connection
• Linear-response range-separated density-functional theory for atomic photoexcitation and photoionization spectra
• Calculating excitation energies by extrapolation along adiabatic connections
• Photoionization and core resonances from range-separated density-functional theory: General formalism and example of the beryllium atom
• Excitation energies from G{ö}rling-Levy perturbation theory along the range-separated adiabatic connection
• Comparison of long-range corrected kernels and range-separated hybrids for excitons in solids
• Photoionization and core resonances from range-separated time-dependent density-functional theory for open-shell states: Example of the lithium atom