Formulation of Quantum Statistical Mechanics Based on the Feynman Path CentroidDensity IV. Algorithms for Centroid Molecular Dynamics

摘要

Numerical algorithms are developed for the centroid molecular dynamics (centroidMD) method to calculate dynamical time correlation functions for general many-body quantum systems. Approaches based on the normal mode path integral molecular dynamics and staging path integral Monte Carlo methods are described to carry out a direct calculation of the force on the centroid variables in the centroid MD algorithm. A more efficient, but approximate, scheme to compute the centroid force is devised which is based on the locally optimized harmonic approximation for the centroid potential. The centroid MD equations in the latter method can be solved with the help of an iterative procedure or through extended Lagrangian dynamics. A third algorithm introduces an effective centroid pseudopotential to approximate the full many-body centroid mean force potential by effective pairwise centroid interactions. Numerical simulations for both prototype models and more realistic many-body systems are performed to explore the feasibility and limitations of each algorithm. Chemical dynamics, Computer simulation, Electrochemistry.