Grassmann extrapolation of density matrices for Born-Oppenheimer molecular dynamics

Abstract

Born-Oppenheimer Molecular Dynamics (BOMD) is a powerful but expensive technique. The main bottleneck in a density functional theory bomd calculation is the solution to the Kohn-Sham (KS) equations, that requires an iterative procedure that starts from a guess for the density matrix. Converged densities from previous points in the trajectory can be used to extrapolate a new guess, however, the non-linear constraint that an idempotent density needs to satisfy make the direct use of standard linear extrapolation techniques not possible. In this contribution, we introduce a locally bijective map between the manifold where the density is defined and its tangent space, so that linear extrapolation can be performed in a vector space while, at the same time, retaining the correct physical properties of the extrapolated density using molecular descriptors. We apply the method to real-life, multiscale polarizable QM/MM.