Comparing Symmetry-Adapted Perturbation Theory to Intermolecular Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals
- 1Department of Chemistry & Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States
- 2Biophysics Graduate Program, The Ohio State University, Columbus, Ohio 43210, United States
Abstract
Energy decomposition analysis (EDA) can provide insight into noncovalent interactions, even though the individual energy components (electrostatics, Pauli repulsion, polarization, dispersion, etc.) are not uniquely defined within quantum mechanics. The present work examines the two titular EDA schemes and elucidates the degree of transferability between their components. We first demonstrate that a many-body dispersion (MBD) model can replace the conventional definition of dispersion in symmetry-adapted perturbation theory (SAPT), preserving reasonable accuracy as compared to third-order SAPT but reducing the computational cost to be comparable to density functional theory (DFT). Individual SAPT + MBD energy components exhibit good correlation with those computed using the absolutely localized molecular orbital (ALMO) EDA scheme, which is built around DFT, such that qualitative explanations and chemical trends are likely to be similar in either approach. SAPT + MBD and ALMO-EDA electrostatic energies are nearly identical, provided that a SAPT-style direct-product reference state is used for ALMO-EDA, but other energy components exhibit substantial quantitative differences. These conclusions hold across a range of density functionals used in the ALMO-EDA calculations, and for different choices of the “dispersion-free” functional that is used to isolate the dispersion energy from the target functional’s interaction energy. The present work provides calibration plots to translate between SAPT + MBD and ALMO-EDA energy components. For a large data set of dimers representing ligand–protein interactions, SAPT + MBD calculations afford superior agreement with the best ab initio benchmarks, as compared to calculations using the state-of-the-art ωB97M-V functional, especially when triple-ζ basis sets are used for SAPT. This conclusion holds even when three-body (Axilrod–Teller–Muto) dispersion corrections are added to the ωB97M-V results.
Versions
Related
- Symmetry-adapted perturbation theory for cavity-modified intermolecular interactions: QED-SAPT0 theory and implementation
- Influence of Small Changes in Intermolecular Distances on Results of Interaction Energy Decomposition for Stacking Interactions, Hydrogen Bonds, and Antiparallel Interactions
- Maximum purity of absolutely separable and absolutely PPT states in qutrit--qudit systems
- Disorder on the hyperbolic square lattice I: Anderson delocalization and absolutely continuous spectrum
- Don't mind the gap: Absolutely Continuous Edge Spectrum in a Mobility Gap
BibTeX
@article{puthillathu2026comparing,
title = {{Comparing Symmetry-Adapted Perturbation Theory to Intermolecular Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals}},
author = {Narayanan Puthillathu and Montgomery Gray and John M. Herbert},
journal = {Journal of Chemical Theory and Computation},
year = {2026},
month = oct,
doi = {10.1021/acs.jctc.6c01446},
url = {https://doi.org/10.1021/acs.jctc.6c01446},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Comparing Symmetry-Adapted Perturbation Theory to Intermolecular Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals
AU - Narayanan Puthillathu
AU - Montgomery Gray
AU - John M. Herbert
PY - 2026
DA - 2026/10/10
JO - Journal of Chemical Theory and Computation
DO - 10.1021/acs.jctc.6c01446
UR - https://doi.org/10.1021/acs.jctc.6c01446
AB - Energy decomposition analysis (EDA) can provide insight into noncovalent interactions, even though the individual energy components (electrostatics, Pauli repulsion, polarization, dispersion, etc.) are not uniquely defined within quantum mechanics. The present work examines the two titular EDA schemes and elucidates the degree of transferability between their components. We first demonstrate that a many-body dispersion (MBD) model can replace the conventional definition of dispersion in symmetry-adapted perturbation theory (SAPT), preserving reasonable accuracy as compared to third-order SAPT but reducing the computational cost to be comparable to density functional theory (DFT). Individual SAPT + MBD energy components exhibit good correlation with those computed using the absolutely localized molecular orbital (ALMO) EDA scheme, which is built around DFT, such that qualitative explanations and chemical trends are likely to be similar in either approach. SAPT + MBD and ALMO-EDA electrostatic energies are nearly identical, provided that a SAPT-style direct-product reference state is used for ALMO-EDA, but other energy components exhibit substantial quantitative differences. These conclusions hold across a range of density functionals used in the ALMO-EDA calculations, and for different choices of the “dispersion-free” functional that is used to isolate the dispersion energy from the target functional’s interaction energy. The present work provides calibration plots to translate between SAPT + MBD and ALMO-EDA energy components. For a large data set of dimers representing ligand–protein interactions, SAPT + MBD calculations afford superior agreement with the best ab initio benchmarks, as compared to calculations using the state-of-the-art ωB97M-V functional, especially when triple-ζ basis sets are used for SAPT. This conclusion holds even when three-body (Axilrod–Teller–Muto) dispersion corrections are added to the ωB97M-V results.
SN - 1549-9618
SN - 1549-9626
ER -