Ab initio dynamics with wave-packets and density matrices

Abstract

Efficient methodologies to conduct simultaneous dynamics of electrons and nuclei are discussed. Particularly, attention is directed to a recent development that combines quantum dynamics with ab initio molecular dynamics. The two components of the methodology, namely, quantum dynamics and ab initio molecular dynamics, are harnessed together using a time-dependent self-consistent field-like coupling procedure. An approach to conduct quantum dynamics using an accurate banded, sparse and Toeplitz representation for the discrete free propagator is highlighted with suitable review of other related approaches. One notable feature of the method is that all important quantum dynamical effects including zero-point effects, tunneling as well as over-barrier reflections are accurately treated. Computational methodologies for improved efficiency of the quantum dynamics are also discussed. There exists a number of ways to carry out simultaneous ab initio molecular dynamics (such as Born–Oppenheimer dynamics and extended Lagrangian dynamics, Car–Parrinello dynamics being a prime example of the latter); our prime focus remains on atom-centered density-matrix propagation and Born–Oppenheimer dynamics. The electronic degrees of freedom are handled at accurate levels of density functional theory, using hybrid or gradient corrected approximations. Benchmark calculations are provided for a prototypical proton transfer system. Future generalizations and goals are discussed.