Direct calculation of dipole moment surfaces through second-order symmetry-adapted perturbation theory for properties
Abstract
Interaction-induced dipole moment surfaces are vital for calculating line intensities and collision-induced absorption coefficients for van der Waals complexes. We introduce the perturbative corrections, of second order with respect to the interaction operator, to the dipole moment (or, in general, any one-electron property) change due to noncovalent interactions. These are obtained in the spirit of the symmetry-adapted perturbation theory for properties (propSAPT) method, developed recently by some of us [B. Tyrcha et al., JCTC 21(9), 4562--4578 (2025)]. When orbital relaxation effects due to the external property field are properly introduced, these can be understood as analytical derivatives of the second-order SAPT interaction energies. We apply the newly introduced formalism to calculations of dipole moment surfaces for three light van der Waals complexes: He...Ar, He...H2 and the H2 dimer. The propSAPT method is compared against finite-field SAPT calculations and finite-field supermolecular CCSD(T) as the reference.
Related
- Comparing Symmetry-Adapted Perturbation Theory to Intermolecular Energy Decomposition Analysis Based on Absolutely Localized Molecular Orbitals
- First-order Degenerate Symmetry-Adapted Perturbation Theory
- Synthesis of colloidal silver-polyphenols nanocomplexes - physicochemical properties, DFT calculation, modeling of adsorption and antibacterial activity
- Linker Symmetry Lowering as a Strategy to Tune Electronic Properties in Two‐Dimensional Conductive MOFs
- PORMAKE2: Topology-Based Generation of Hypothetical Metal-Organic Frameworks through Single-Metal Nodes and Symmetry-Aware Linker Rotation
BibTeX
@misc{tyrcha2026direct,
title = {{Direct calculation of dipole moment surfaces through second-order symmetry-adapted perturbation theory for properties}},
author = {Bartosz Tyrcha and Marcin Stachowiak and Konrad Patkowski and Piotr S. Żuchowski},
howpublished = {arXiv},
year = {2026},
month = nov,
doi = {10.48550/arxiv.2611.07993},
eprint = {2611.07993},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2611.07993},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Direct calculation of dipole moment surfaces through second-order symmetry-adapted perturbation theory for properties
AU - Bartosz Tyrcha
AU - Marcin Stachowiak
AU - Konrad Patkowski
AU - Piotr S. Żuchowski
PY - 2026
DA - 2026/11/05
PB - arXiv
DO - 10.48550/arxiv.2611.07993
UR - https://arxiv.org/abs/2611.07993
AB - Interaction-induced dipole moment surfaces are vital for calculating line intensities and collision-induced absorption coefficients for van der Waals complexes. We introduce the perturbative corrections, of second order with respect to the interaction operator, to the dipole moment (or, in general, any one-electron property) change due to noncovalent interactions. These are obtained in the spirit of the symmetry-adapted perturbation theory for properties (propSAPT) method, developed recently by some of us [B. Tyrcha et al., JCTC 21(9), 4562--4578 (2025)]. When orbital relaxation effects due to the external property field are properly introduced, these can be understood as analytical derivatives of the second-order SAPT interaction energies. We apply the newly introduced formalism to calculations of dipole moment surfaces for three light van der Waals complexes: He...Ar, He...H_2 and the H_2 dimer. The propSAPT method is compared against finite-field SAPT calculations and finite-field supermolecular CCSD(T) as the reference.
ER -