Boundary based on exchange symmetry theory for multilevel simulations, 2; Multiple time scale approach

Shiga, Motoyuki   ; Masia, M.*

The boundary condition based on exchange symmetry theory for QM/MM method has been applied to simulate the whole series of hydrated alkali ions. In this article we show how to overcome the sampling bottleneck for QM/MM simulations by using our method with multiple time scale algorithm. We extend it the use of ab initio QM/MM path integral molecular dynamics simulations, thus demonstrating that one could obtain a complete quantum description of the primary subsystem based on first principles. We show that it is important to account for electron correlation to better reproduce the hydration structural properties such as the ion-water radial distribution functions, and the anisotropic angular distributions around the ion.