Autoionizing Resonances in Time-Dependent Density Functional Theory

TL;DR

This paper advances TDDFT by developing frequency-dependent kernels to accurately describe autoionizing resonances, including Fano lineshapes, especially for bound double excitations.

Contribution

It introduces a Fano TDDFT kernel and a dressed kernel to improve the description of autoionizing resonances in TDDFT, addressing limitations of adiabatic approximations.

Findings

Fano lineshape can be reproduced within TDDFT using the new kernel.

Frequency-dependent kernels are essential for bound double excitations.

The approximation is exact in the weak interaction limit for isolated resonances.

Abstract

Autoionizing resonances that arise from the interaction of a bound single-excitation with the continuum can be accurately captured with the presently used approximations in time-dependent density functional theory (TDDFT), but those arising from a bound double excitation cannot. In the former case, we explain how an adiabatic kernel, which has no frequency-dependence, can yet generate the strongly frequency-dependent resonant structures in the interacting response function, not present in the Kohn-Sham response function. In the case of the bound double-excitation, we explain that a strongly frequency-dependent kernel is needed, and derive one for the vicinity of a resonance of the latter type, as an {\it a posteriori} correction to the usual adiabatic approximations in TDDFT. Our approximation becomes exact for an isolated resonance in the limit of weak interaction, where one discrete state interacts with one continuum. We derive a "Fano TDDFT kernel" that reproduces the Fano lineshape within the TDDFT formalism, and also a dressed kernel, that operates on top of an adiabatic approximation. We illustrate our results on a simple model system.