Assessment of SAPT and Supermolecular EDAs Approaches for the Development of Separable and Polarizable force fields - Archive ouverte HAL Access content directly
Journal Articles Journal of Chemical Theory and Computation Year : 2021

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

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 ωB97X-D||ALMO are the most accurate and reliable techniques

Dates and versions

hal-02912013 , version 1 (05-08-2020)

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Sehr Naseem-Khan, Nohad Gresh, Alston J. Misquitta, Jean-Philip Piquemal. Assessment of SAPT and Supermolecular EDAs Approaches for the Development of Separable and Polarizable force fields. Journal of Chemical Theory and Computation, 2021, 17 (5), pp.2759-2774. ⟨10.1021/acs.jctc.0c01337⟩. ⟨hal-02912013⟩
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