Completely Multipolar Model as a General Framework for Many-Body Interactions as Illustrated for Water

TL;DR

The paper introduces the Completely Multipolar Model (CMM), a comprehensive framework for many-body interactions in molecules like water, ensuring accurate energy decomposition and physical property reproduction across various configurations.

Contribution

The CMM provides a unified, functional form-based approach to model all intermolecular energy terms with correct asymptotic behavior and explicit many-body charge transfer, improving upon existing models.

Findings

Accurately reproduces water cluster energies and geometries.

Ensures correct asymptotic behavior of interaction terms.

Reproduces monomer properties such as dipole moments and polarizabilities.

Abstract

We introduce a general framework for many-body force field models, the Completely Multipolar Model (CMM), that utilizes multipolar electrical moments modulated by exponential decay of electron density as a common functional form for all piecewise terms of an energy decomposition analysis of intermolecular interactions. With this common functional form the CMM model establishes well-formulated damped tensors that reach the correct asymptotes at both long- and short-range while formally ensuring no short-range catastrophes. The CMM describes the separable EDA terms of dispersion, exchange polarization, and Pauli repulsion with short-ranged anisotropy, polarization as intramolecular charge fluctuations and induced dipoles, while charge transfer describes explicit movement of charge between molecules, and naturally describes many-body charge transfer by coupling into the polarization equations. We also utilize a new one-body potential that accounts for intramolecular polarization by including an electric field-dependent correction to the Morse potential to ensure that the CMM reproduces all physically relevant monomer properties including the dipole moment, molecular polarizability, and dipole and polarizability derivatives. The quality of the CMM is illustrated through agreement of individual terms of the EDA and excellent extrapolation to energies and geometries of an extensive validation set of water cluster data.