An Efficient Linear-Scaling Electrostatic Coupling for Treating Periodic Boundary Conditions in QM/MM Simulations
Abstract
A new linear-scaling method based on a multigrid approach to treat long-range electrostatic interactions in hybrid quantum mechanics/molecular mechanics (QM/MM) simulations is described. The scheme has been implemented in the context of a QM calculation based on density functional theory (DFT). The method is tested on an analytical model to validate the new algorithm. Two realistic problems in α-quartz crystals and a zwitterionic dipeptide (GLY-ALA) in water have been chosen as further tests. Results from QM/MM calculations with periodic boundary conditions (PBC) show that the use of PBC is essential when studying highly ordered crystal structures, unless a carefully designed MM crystal is used for the calculation. With a general shaped MM subsystem, the absence of PBC leads to an incorrect description of Kohn−Sham band gaps and charge density. The present method allows periodic boundary conditions to be used in molecular simulations of biological and material science systems.
*
Corresponding author fax: +41919138817; e-mail: [email protected].
†
Scuola Normale Superiore di Pisa.
‡
ETH Zürich.
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