Modeling core-hole screening in jellium clusters using density functional theory

TL;DR

This paper investigates core-hole screening in sodium clusters using density functional theory, revealing how screening dynamics occur on attosecond time scales and depend on cluster size and photon energy.

Contribution

It introduces a detailed analysis of core-hole screening timescales in metal clusters using time-dependent DFT, linking theoretical predictions with recent experimental observations.

Findings

Screening occurs on two distinct time scales: tens of attoseconds for core-shell electrons and hundreds for valence electrons.

Relaxed binding energies follow the metal-sphere behavior, matching experimental results for large clusters.

Unrelaxed energies and Kohn-Sham orbital energies do not accurately predict photoelectron kinetic energies.

Abstract

The screening of a 2p core-hole in Na clusters is investigated using density functional theory applied to an extended jellium model with an all-electron atom in the center. The study is related to recent experiments at the free electron laser at DESY in which photoelectron spectra from mass-selected, core-shell ionized metal clusters have been recorded. Relaxed and unrelaxed binding energies as well as Kohn-Sham orbital energies are calculated in Perdew-Zunger self-interaction-corrected exchange-only local spin-density approximation for valence and 2p core electrons in Na clusters up to 58 atoms. The relaxed binding energies follow approximately the metal-sphere behavior. The same behavior is seen in the experiment for sufficiently big clusters, indicating perfect screening and that the relaxation energy due to screening goes to the photoelectron. Instead, calculating the kinetic energy of the photoelectrons using unrelaxed binding energies or Kohn-Sham orbital energies yields wrong results for core-shell electrons. The screening {\em dynamics} are investigated using time-dependent density functional theory. It is shown that screening occurs on two time scales, a core-shell-dependent inner-atomic and an inter-atomic valence electron time scale. In the case of Na 2p ionization the remaining electrons in the 2p shell screen within tens of attoseconds while the screening due to cluster valence electrons occurs within several hundreds of attoseconds. The screening time-scales may be compared to the photon energy and cluster size-dependent escape times of the photoelectron in order to estimate whether the photoelectron is capable of picking up the relaxation energy or whether the residual system is left in an excited state.