Assessment of SAPT and Supermolecular EDAs Approaches for the Development of Separable and Polarizable force fields

TL;DR

This paper systematically compares SAPT and supermolecular EDA methods to identify the most accurate approaches for developing polarizable force fields, using challenging water complexes as test cases.

Contribution

It provides a detailed assessment of SAPT and EDA variants, introducing a procedure to separate induction energy components for better force field development.

Findings

SAPT(DFT) and ALMO are the most accurate methods.

SAPT(DFT) effectively separates polarization and charge-delocalization energies.

The study highlights the strengths and limitations of each approach.

Abstract

What is the best reference quantum chemical approach to decipher the energycomponents of the total interaction energy : Symmetry-Adapted Perturbation Theory(SAPT) or Supermolecular Energy Decomposition Analysis (EDA) methods? With the rise of physically motivated polarizable force fields (polFF) grounded on these procedures, the need to answer such a question becomes critical. these procedures, the need to answer such a question becomes critical. We report a systematic and detailed assessment of three variants of SAPT (namely SAPT(2), SAPT(2+3) and SAPT(DFT) and three supermolecular EDAs approaches (ALMO, CSOV and RVS). A set of challenging, strongly bound water complexes: (H2O)2, (Zn2+)H2O and F-)H2O are used as stress-tests for these electronic structure methods. We have developed a procedure to separate the induction energy into the polarization and charge-delocalization using an infinite-order strategy based on SAPT(DFT). This paper aims to provide an overview of the capabilities and limitations, but also similarities, of SAPT and supermolecular EDAs approaches for polFF developments. Our results show that SAPT(DFT)/noS**2 and {\omega}B97X-D||ALMO are the most accurate and reliable techniques