Photoemission spectra from the Extended Koopman's Theorem, revisited

TL;DR

This paper revisits the Extended Koopman's Theorem (EKT) by linking it with the many-body effective energy theory (MEET), enabling improved calculation of photoemission spectra and spectral functions.

Contribution

It establishes a connection between EKT and MEET, allowing for enhanced spectral function calculations and basis set optimization.

Findings

EKT and MEET are linked through their lowest approximation levels.

The approach enables calculation of the full spectral function.

Illustrated with Hubbard dimer and bulk silicon examples.

Abstract

The Extended Koopman's Theorem (EKT) provides a straightforward way to compute charged excitations from any level of theory. In this work we make the link with the many-body effective energy theory (MEET) that we derived to calculate the spectral function, which is directly related to photoemission spectra. In particular, we show that at its lowest level of approximation the MEET removal and addition energies correspond to the so-called diagonal approximation of the EKT. Thanks to this link, the EKT and the MEET can benefit from mutual insight. In particular, one can readily extend the EKT to calculate the full spectral function, and choose a more optimal basis set for the MEET by solving the EKT secular equation. We illustrate these findings with the examples of the Hubbard dimer and bulk silicon.