Tension between predicting accurate ground state correlation energies and excitation energies from adiabatic approximations in TDDFT

摘要

The connection between the adiabatic excitation energy of time-dependent density functional theory and the ground state correlation energy from the adiabatic connection fluctuation-dissipation theorem (ACFDT) is explored in the limiting case of one excited state. An exact expression is derived for any adiabatic Hartree-exchange-correlation kernel that connects the excitation energy and the potential contribution to correlation. The resulting formula is applied to the asymmetric Hubbard dimer, a system where this limit is exact. Results from a hierarchy of approximations to the kernel, including the random phase approximation (RPA) with and without exchange and the adiabatically exact (AE) approximation, are compared to the exact ones. At full coupling, the numerical results indicate a tension between predicting an accurate excitation energy and an accurate potential contribution to correlation. The AE approximation is capable of making accurate predictions of both quantities, but only in parts of the parameter space that classify as weakly correlated, while RPA tends to be unable to accurately predict these properties simultaneously anywhere. For a strongly correlated dimer, the AE approximation greatly overestimates the excitation energy yet continues to yield an accurate ground state correlation energy due to its accurate prediction of the adiabatic connection integrand. If similar trends hold for real systems, the development of correlation kernels will be important for applications of the ACFDT in systems with large potential contributions to correlation.