Nonlocal and nonadiabatic Pauli potential for time-dependent orbital-free density functional theory

TL;DR

This paper introduces a nonlocal, nonadiabatic Pauli potential for time-dependent orbital-free density functional theory, enhancing its accuracy for metallic and semiconductor systems in simulating electronic dynamics.

Contribution

It proposes a novel nonlocal, nonadiabatic Pauli potential based on time-dependent densities, improving TD-OFDFT's accuracy for large systems.

Findings

Accurately models optical spectra of metallic clusters

Semiquantitative results for semiconductor clusters

Enables wider application of TD-OFDFT in nonequilibrium dynamics

Abstract

Time-dependent orbital-free density functional theory (TD-OFDFT) is an efficient ab-initio method for calculating the electronic dynamics of large systems. In comparison to standard TD-DFT, it computes only a single electronic state regardless of system size, but it requires an additional time-dependent Pauli potential term. We propose a nonadiabatic and nonlocal Pauli potential whose main ingredients are the time-dependent particle and current densities. Our calculations of the optical spectra of metallic and semiconductor clusters indicate that nonlocal and nonadiabatic TD-OFDFT performs accurately for metallic systems and semiquantitatively for semiconductors. This work opens the door to wide applicability of TD-OFDFT for nonequilibrium electron and electron-nuclear dynamics of materials.