What Is the Accuracy Limit of Adiabatic Linear-Response TDDFT Using Exact Exchange-Correlation Potentials and Approximate Kernels?

摘要

Calculation of vertical excitation energies by the adiabatic linear-response time-dependent density-functional theory (TDDFT) requires static Kohn-Sham potentials and exchange-correlation kernels. When these quantities are derived from standard density-functional approximations DFA), mean absolute errors (MAE) of the method are known to range from 0.2 eV to over 1 eV, depending on the functional and type of excitation. We investigate how the performance of TDDFT varies when increasingly accurate exchange-correlation potentials derived from Hartree-Fock HF) and post-HF wavefunctions are combined with different approximate kernels. The lowest MAEs obtained in this manner for valence excitations are about 0.15-0.2 eV, which appears to be the practical limit of the accuracy of TDDFT that can be achieved by improving the Kohn-Sham potentials alone. These findings are consistent with previous reports on the benefits of accurate exchange-correlation potentials in TDDFT, but provide new insights and afford more definitive conclusions.