A Quantum-Mechanics Molecular-Mechanics scheme for extended systems

TL;DR

This paper presents a hybrid quantum-mechanics molecular-mechanics (QM-MM) approach for periodic systems that improves computational efficiency and accuracy in simulating complex condensed matter systems, including interfaces and nanoconfined fluids.

Contribution

It introduces a novel QM-MM scheme for periodic systems using planewave DFT, treating MM atoms as fractional charged ions within the same supercell, simplifying electrostatics and enabling efficient simulations.

Findings

The method accurately reproduces energetic, structural, and dynamical properties of water systems.

It achieves substantial computational savings for systems of a few hundred atoms.

Vibrational spectra of water at TiO₂ interfaces are effectively modeled.

Abstract

We introduce and discuss a hybrid quantum-mechanics molecular-mechanics (QM-MM) approach for Car-Parrinello DFT simulations with pseudopotentials and planewaves basis, designed for the treatment of periodic systems. In this implementation the MM atoms are considered as additional QM ions having fractional charges of either sign, which provides conceptual and computational simplicity by exploiting the machinery already existing in planewave codes to deal with electrostatics in periodic boundary conditions. With this strategy, both the QM and MM regions are contained in the same supercell, which determines the periodicity for the whole system. Thus, while this method is not meant to compete with non-periodic QM-MM schemes able to handle extremely large but finite MM regions, it is shown that for periodic systems of a few hundred atoms, our approach provides substantial savings in computational times by treating classically a fraction of the particles. The performance and accuracy of the method is assessed through the study of energetic, structural, and dynamical aspects of the water dimer and of the aqueous bulk phase. Finally, the QM-MM scheme is applied to the computation of the vibrational spectra of water layers adsorbed at the TiO$_2$ anatase (101) solid-liquid interface. This investigation suggests that the inclusion of a second monolayer of H$_2$O molecules is sufficient to induce on the first adsorbed layer, a vibrational dynamics similar to that taking place in the presence of an aqueous environment. The present QM-MM scheme appears as a very interesting tool to efficiently perform molecular dynamics simulations of complex condensed matter systems, from solutions to nanoconfined fluids to different kind of interfaces.