2024/10/03 by Caroline S. Glick, Asem Alenaizan, Daniel L. Cheney +2 · 1 voice
Chemistry · Engineering · Physics and Astronomy · #Molecular Junctions and Nanostructures #Photochemistry and Electron Transfer Studies #Spectroscopy and Quantum Chemical Studies
paper · doi:10.1063/5.0221974
openalex publication_date 2024/10/03 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/13
Symmetry-adapted perturbation theory (SAPT) is an ab initio approach that directly computes noncovalent interaction energies in terms of electrostatics, exchange repulsion, induction/polarization, and London dispersion components. Due to its high computational scaling, routine applications of even the lowest order of SAPT are typically limited to a few hundred atoms. To address this limitation, we report here the addition of electrostatic embedding to the SAPT (EE-SAPT) and ISAPT (EE-ISAPT) methods. We illustrate the embedding scheme using water trimer as a prototype example. Then, we show that EE-SAPT/EE-ISAPT can be applied for efficiently and accurately computing noncovalent interactions in large systems, including solvated dimers and protein-ligand systems. In the latter application, particular care must be taken to properly handle the quantum mechanics/molecular mechanics boundary when it cuts covalent bonds. We investigate various schemes for handling charges near this boundary and demonstrate which are most effective in the context of charge-embedded SAPT.