Shadow Molecular Dynamics for Flexible Multipole Models

Abstract: Shadow molecular dynamics provide an efficient and stable atomistic simulation framework for flexible charge models with long-range electrostatic interactions. While previous implementations have been limited to atomic monopole charge distributions, we extend this approach to flexible multipole models. We derive detailed expressions for the shadow energy functions, potentials, and force terms, explicitly incorporating monopole-monopole, dipole-monopole, and dipole-dipole interactions. In our formulation, both atomic monopoles and atomic dipoles are treated as extended dynamical variables alongside the propagation of the nuclear degrees of freedom. We demonstrate that introducing the additional dipole degrees of freedom preserves the stability and accuracy previously seen in monopole-only shadow molecular dynamics simulations. Additionally, we present a shadow molecular dynamics scheme where the monopole charges are held fixed while the dipoles remain flexible. Our extended shadow dynamics provide a framework for stable, computationally efficient, and versatile molecular dynamics simulations involving long-range interactions between flexible multipoles. This is of particular interest in combination with modern artificial intelligence and machine learning techniques, which are increasingly used to develop physics-informed and data-driven foundation models for atomistic simulations. These models aim to provide transferable, high-accuracy representations of atomic interactions that are applicable across diverse sets of molecular systems, which requires accurate treatment of long-range charge interactions.