English

Fast and Accurate Charge Transfer Excitations via Nested Aufbau Suppressed Coupled Cluster

Chemical Physics 2025-07-28 v2

Abstract

Modeling charge transfer well can require treating post-excitation orbital relaxations and handling medium to large molecules in realistic environments. By combining a state-specific correlation treatment with such orbital relaxations, Aufbau suppressed coupled cluster has proven accurate for charge transfer, but, like many coupled cluster methods, it struggles with large system sizes. We derive a low-cost Aufbau suppressed second order perturbation theory and show that, by nesting a small coupled cluster treatment inside of it, computational cost and scaling are reduced while accuracy is maintained. Formal asymptotic costs are dropped from iterative N6N^6 to non-iterative N5N^5 plus iterative N3N^3, and we test an initial implementation that can handle about 100 atoms and 800 orbitals on a single computational node. Charge transfer excitation energy errors are typically below 0.1 eV on average, with an average 0.25 eV improvement over N6N^6-cost equation of motion coupled cluster with singles and doubles.

Keywords

Cite

@article{arxiv.2505.17299,
  title  = {Fast and Accurate Charge Transfer Excitations via Nested Aufbau Suppressed Coupled Cluster},
  author = {Harrison Tuckman and Eric Neuscamman},
  journal= {arXiv preprint arXiv:2505.17299},
  year   = {2025}
}

Comments

21 pages, 7 figures