Exploring electron affinities, LUMO energies, and band gaps with electron-pair theories

TL;DR

This paper introduces the EA-EOM-pCCD method, a computational approach for accurately and efficiently calculating electron affinities, LUMO energies, and electron attachment spectra, with applications to organic molecules and uranyl dichloride.

Contribution

The paper presents a novel EA-EOM-pCCD ansatz that improves the accuracy and efficiency of computing electron affinities and unoccupied orbital energies compared to existing methods.

Findings

EA-EOM-pCCD provides more reliable LUMO energies than ionization potential EOM for HOMO.

The method achieves near chemical accuracy for EAs of rylene derivatives.

EA-EOM-pCCD accurately models electron attachment in uranyl dichloride.

Abstract

We introduce the electron attachment equation-of-motion pair coupled cluster doubles (EA-EOM-pCCD) ansatz, which allows us to inexpensively compute electron affinities, energies of unoccupied orbitals, and electron attachment spectra. We assess the accuracy of EA-EOM-pCCD for a representative data set of organic molecules for which experimental data is available, as well as the electron attachment process in uranyl dichloride. EA-EOM-pCCD provides more reliable energies for the LUMO than its ionization potential EOM counterpart for the HOMO. The advantage of EA-EOM-pCCD is demonstrated for rylene and rylene diimide units of different chain lengths, where the differences between theoretical and experimental EAs approach chemical accuracy.