Ab initio path integral molecular dynamics: Basic ideas

Abstract

The essential ideas underlying ab initio path integral molecular dynamics and its efficient numerical implementation are discussed. In this approach the nuclei are treated as quantum particles within the path integral formulation of quantum statistical mechanics. The electronic degrees of freedom are treated explicitly based on state-of-the-art electronic structure theory. This renders ab initio simulations of quantum systems possible without recourse to model potentials. A combined extended Lagrangian for both quantum nuclei and electrons defines a dynamical system and yields molecular dynamics trajectories that can be analyzed to obtain quantum statistical expectation values of time-independent operators. The methodology can be applied to a wide range of fields addressing problems in molecular and condensed matter chemistry and physics.