First-Principles Many-Body Nonadditive Polarization Energies from Monomer and Dimer Calculations Only: A Case Study on Water

Abstract

The many-body polarization energy is the major source of non-additivity in strongly polar systems such as water. This non-additivity is often considerable and must be included, if only in an average manner, to correctly describe the physical properties of the system. Models for the polarization energy are usually parameterized using experimental data, or theoretical estimates of the many-body effects. Here we show how many-body polarization models can be developed for water complexes using data for the monomer and dimer only using ideas recently developed in the field of intermolecular perturbation theory and state-of-the-art approaches for calculating distributed molecular properties based on the iterated stockholder atoms (ISA) algorithm. We show how these models can be calculated, and validate their accuracy in describing the many-body non-additive energies of a range of water clusters. We further investigate their sensitivity to the details of the polarization damping models used. We show how our very best polarization models yield many-body energies that agree with those computed with coupled-cluster methods, but at a fraction of the computational cost.

A non-empirical intermolecular force-field for trinitrobenzene and its application in crystal structure prediction

“…Note that, in principle, the damping parameters are dependent on the sites involved. Indeed, this has been demonstrated for the water dimer, 4 but due to limitations of the DMACRYS 14 code, here, we are restricted to single damping parameters for the polarization and dispersion models. This results in a degradation of the quality of the resulting models and the need for compromises.…”

“…This CamCASP-derived TNB DIFF model is the first time the ISA partitioning of the molecular charge density into atoms has been used for all the components of the potential for a molecule larger than water. 4 These atomic charge densities were used to derive the atomic multipoles, 44 polarizabilities, 59 and dispersion 59 parameters and, via the distributed density overlap model, to provide a first estimate of the repulsion potentials and form of anisotropy. 16 The more rigorous ISA partitioning method provides maximally spherical atoms, thus minimizing the number of important anisotropy terms.…”

“…6,7 As the charge densities of closed shell organic molecules are only slightly perturbed by intermolecular interactions, their intermolecular forces are well described by perturbation methods. Indeed, perturbational methods such as symmetry-adapted perturbation theory (SAPT), 4,8,9 and its variant based on density-functional theory [SAPT(DFT)], 6,7 are ideally suited for this problem as they are not only accurate, and also, SAPT(DFT) is computationally efficient. Additionally, perturbation theory provides a rigorous match between the short-range energies and the long-range analytic expansions using multipoles, polarizabilities, and dispersion coefficients.…”

Development of the Quantum Inspired SIBFA Many-Body Polarizable Force Field: Enabling Condensed Phase Molecular Dynamics Simulations

“…[8][9][10][11][12][13][14] The description of water with a polFF is challenging 15 as it requires a detailed understanding of its intermolecular interactions, and is also a marker of its predictive ability. Several polarizable water models were recently reported (not all suitable for MD simulations), grounded either on Energy Decomposition Analysis (EDA) methods, such as the MB-UCB-MDQ 16 water model using the Absolutely Delocalized Molecular Orbital (ALMO), 17 or grounded on Symmetry Adapted Perturbation Theory (SAPT) 18,19 such as EFP (Effective Fragment Potential), 20,21 the polarizable SAPT-5, 22 MB-POL, 23 Distributed Point Polarizable model (DPP), 24 Gaussian Electrostatic Model (GEM), 14,[25][26][27] Hydrogen-like Intermolecular Polarizable POtential (HIPPO 28 ), Derived Intermolecular Force-Field (DIFF), 29 AMOEBA+ (Atomic Multipole Optimized Energetics for Biomolecular Simulation +), 11,12 and others.…”

Assessment of SAPT and Supermolecular EDA Approaches for the Development of Separable and Polarizable Force Fields

“…There is evidence that the definition of the polarization energy, that is the induction energy free of charge-delocalization, is essential for developing accurate many-body polarization models. [21][22][23] Therefore, Stone and Misquitta 24 have proposed a basis-space approach to partition the second-and third-order induction energies into contributions from the polarization and charge-delocalization energies. Subsequently, Misquitta 25 proposed to use a regularization scheme to partition the second-order induction energy into its CD and POL parts.…”