English

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

Chemical Physics 2024-06-24 v1

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.

Keywords

Cite

@article{arxiv.2406.14716,
  title  = {Exploring electron affinities, LUMO energies, and band gaps with electron-pair theories},
  author = {Marta Gałyńska and Paweł Tecmer and Katharina Bogusławski},
  journal= {arXiv preprint arXiv:2406.14716},
  year   = {2024}
}

Comments

5 pages, 3 graphs