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

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.

5 pages, 3 graphs

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Cited by in corpus (3)

• Simple and efficient computational strategies for calculating orbital energies and pair-orbital energies from pCCD-based methods
• Tuning Domain-Based Charge Transfer in Organic Dyes: Impact of Heteroatom Doping on the $\pi$-Linker of Carbazole-Based Systems
• Ionization Potentials at Mean-Field Computational Cost: The Extended Koopmans' Framework for pCCD