Uncoupled fragment electric-field response functions: An accelerated model for the polarization energy in energy decomposition analysis of intermolecular interactions

Energy decomposition analysis (EDA) has become an important tool to relate electronic structure calculations to physically meaningful contributions. The second generation of the absolutely localized molecular orbitals (ALMO-EDA) accounts for polarization with a well-defined basis set limit using tru...

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Bibliographic Details
Published in:Chemical physics letters 2025-03, Vol.862, p.141825, Article 141825
Main Authors: Aldossary, Abdulrahman, Shen, Hengyuan, Wang, Zhenling, Head-Gordon, Martin
Format: Article
Language:English
Subjects:
Density functional theory
Energy decomposition analysis
Intermolecular interactions
Polarization
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Summary:Energy decomposition analysis (EDA) has become an important tool to relate electronic structure calculations to physically meaningful contributions. The second generation of the absolutely localized molecular orbitals (ALMO-EDA) accounts for polarization with a well-defined basis set limit using truncated virtual orbitals, namely fragment electric-field response functions (FERF). In this work, we introduce a hessian-free uncoupled FERF (uFERF) alternative that has very similar accuracy and is 5–10 times faster to evaluate. Furthermore, we investigate the use of monopole uFERFs (response to scaled nuclear charges) for intermolecular interactions and establish their role in strong ion-neutral interactions. [Display omitted] •Well-defined polarization energy in energy decomposition analysis.•Fast and accurate uncoupled fragment electric-field response functions.•Monopole uFERFs are important for strong ion-neutral interactions.
ISSN:0009-2614
DOI:10.1016/j.cplett.2024.141825