Testing exact-factorization-based density functional approximation on a continuous density model
In this work, we test the performance of an exact-factorization-based density functional approximation (DFA) for electron-nuclear correlation beyond the Born-Oppenheimer approximation that was derived in Li et al. [J. Chem. Phys.148, 084110 (2018)]. The present work extends beyond the Hubbard model that was used previously in a two-electron Shin-Metiu model with continuous electronic density in one dimension. Using new iteration techniques, we managed to solve coupled Kohn-Sham equations that embody nonadiabatic corrections with a nuclear Schrödinger equation. Our results show that the DFA can successfully capture the nonadiabatic effect caused by electron-nuclear correlation as manifested in the correct shift of the critical nuclear position where the proton-coupled electron transfer takes place. The nonadiabatic correction to the Kohn-Sham potential also leads to a shift of orbital energies, which can potentially be useful to study band renormalization induced by electron-phonon interactions in bulk materials.
Authors
- Y. Li (ORCID: https://orcid.org/0009-0002-3300-3841)
- Chen Li (ORCID: https://orcid.org/0000-0003-2115-8694)
- Zixuan Wang (ORCID: https://orcid.org/0000-0002-6694-6558)
Institutions
- Peking University (CN)
- Beijing National Laboratory for Molecular Sciences (CN)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2025-06-16
- DOI
- https://doi.org/10.1063/5.0260749
- Primary Topic
- Advanced Chemical Physics Studies
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Natural Science Foundation of China
- National Key Research and Development Program of China