Exchange kernel $f^h_x(q,\omega)$ of electron liquid from the variational principle of McLachlan

TL;DR

This paper investigates the exchange kernel of the electron liquid derived from McLachlan's variational principle, showing it accurately captures exchange effects and complements existing kernels in time-dependent density functional theory.

Contribution

It demonstrates that the McLachlan variational principle yields an exchange kernel that accurately reproduces exchange effects in the electron liquid, filling gaps left by constraint-based kernels.

Findings

The McLVP-based exchange kernel accurately reproduces exchange features.

It accounts for exchange effects without including correlations.

Combining McLVP and constraint-based kernels can improve TDDFT performance.

Abstract

By minimizing, in the $L_2$ norm, the difference between the left- and the right-hand sides of the time-dependent Schr\"{o}dinger equation, the variational principle of McLachlan (McLVP) [A. McLachlan, Molecular Physics {\bf 8}, 39 (1964)] provides a powerful tool for the generation of equations of motion. If the trial wave function is the Slater determinant, McLVP produces a temporally and spatially nonlocal exchange potential [V. U. Nazarov, Phys. Rev. B {\bf 87}, 165125 (2013)]. We study the performance of the corresponding wave-vector and frequency-dependent exchange kernel $f^h_x(q,\omega)$ of the homogeneous electron liquid. While the McLVP-based $f^h_x(q,\omega)$ lacks correlations by construction, we find that it accurately accounts for exchange, reproducing features in the quantum Monte Carlo data, which the known constraint-based kernels miss. We argue that the complementary use of the McLVP- and the constraint-based exchange-correlation kernels will enhance the performance of the linear response time-dependent density functional theory of the electron liquid.