Insights From Exact Exchange-Correlation Kernels

TL;DR

This paper computes the exact exchange-correlation kernel in time-dependent density functional theory for one-dimensional systems, revealing its frequency dependence and implications for approximations and optical spectra.

Contribution

It provides the first detailed numerical analysis of the exact $f_ ext{xc}$ over a wide frequency range, highlighting its structure and limitations of common approximations.

Findings

$f_ ext{xc}$ is largely frequency independent near low-energy excitations.

Exact $f_ ext{xc}$ captures double excitations through singularities.

Adiabatic approximation effectively describes lowest transitions.

Abstract

The exact exchange-correlation (xc) kernel $f_\mathrm{xc}(x,x',\omega)$ of linear response time-dependent density functional theory is computed over a wide range of frequencies, for three canonical one-dimensional finite systems. Methods used to ensure the numerical robustness of $f_\mathrm{xc}$ are set out. The frequency dependence of $f_\text{xc}$ is found to be due largely to its analytic structure, i.e. its singularities at certain frequencies, which are required in order to capture particular transitions, including those of double excitation character. However, within the frequency range of the first few interacting excitations, $f_\mathrm{xc}$ is approximately frequency independent, meaning the exact adiabatic approximation $f_\mathrm{xc}(\omega = 0)$ remedies the failings of the local density approximation and random phase approximation for these lowest transitions. The key differences between the exact $f_\mathrm{xc}$ and its common approximations are analyzed, and cannot be eliminated by exploiting the limited gauge freedom in $f_\mathrm{xc}$. The optical spectrum benefits from using as accurate as possible an $f_\mathrm{xc}$ and ground-state xc potential, while maintaining exact compatibility between the two is of less importance.