Exact-exchange optimized effective potential and memory effect in time-dependent density functional theory

Abstract

The memory effect in time-dependent density functional theory (TDDFT) is important in simulating many time-dependent physical processes, and its implementation in real time has been a longstanding challenge, thus limiting most of TDDFT applications to either adiabatic or linear-response regime. In this paper, we conduct the non-adiabatic calculations for a one-dimensional two-electron Helium model in a triplet state using the recently formulated Sturm-Liouville-type time-local equation for the time-dependent optimized effective potential (TDOEP) with the exact exchange functional, and the results agree with the exact time-dependent Schrodinger equation solutions. It is also found that the time-dependent dipole moment and probability density calculated from the TDOEP approach are more accurate than those from the adiabatic time-dependent Krieger-Li-Iafrate (TDKLI) approximation and the adiabatic local spin density approximation. Specifically, the non-adiabatic and memory-dependent terms in the time-local TDOEP equation correctly describe the time-dependent structure of exchange-correlation potential and yield the probability density evolution. These findings should provide important insights toward future studies on memory effects in TDDFT.