A Versatile Multiple Time Step Scheme for Efficient ab Initio Molecular Dynamics Simulations

We present here our implementation of a time-reversible, multiple time step (MTS) method for full QM and hybrid QM/MM Born–Oppenheimer molecular dynamics simulations. The method relies on a fully flexible combination of electronic structure methods, from density functional theory to wave function-based quantum chemistry methods, to evaluate the nuclear forces in the reference and in the correction steps. The possibility of combining different electronic structure methods is based on the observation that exchange and correlation terms only contribute to low frequency modes of nuclear forces. We show how a pair of low/high level electronic structure methods that individually would lead to very different system properties can be efficiently combined in the reference and correction steps of this MTS scheme. The current MTS implementation makes it possible to perform highly accurate ab initio molecular dynamics simulations at reduced computational cost. Stable and accurate trajectories were obtained with time steps of several femtoseconds, similar to and even exceeding the ones usually adopted in classical molecular dynamics, in particular when using a generalized Langevin stochastic thermostat. Compared to the standard Velocity Verlet integration, the present MTS scheme allows for a 5- to 6-fold overall speedup, at an unaltered level of accuracy.