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

2024/06/20 by Gałyńska, Marta, Tecmer, Paweł, Bogusławski, Katharina · 3 citations
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences

paper · doi:10.48550/arxiv.2406.14716

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.

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