title: Accelerating the convergence of path integral dynamics with a generalized Langevin equation.
abstract: The quantum nature of nuclei plays an important role in the accurate modelling of light atoms such as hydrogen, but it is often neglected in simulations due to the high computational overhead involved. It has recently been shown that zero-point energy effects can be included comparatively cheaply in simulations of harmonic and quasiharmonic systems by augmenting classical molecular dynamics with a generalized Langevin equation (GLE). Here we describe how a similar approach can be used to accelerate the convergence of path integral (PI) molecular dynamics to the exact quantum mechanical result in more strongly anharmonic systems exhibiting both zero point energy and tunnelling effects. The resulting PI-GLE method is illustrated with applications to a double-well tunnelling problem and to liquid water.
authors.affiliation: Computational Science, Department of Chemistry and Applied Biosciences, ETH Zürich, Lugano, Switzerland. michele.ceriotti@phys.chem.ethz.ch
authors.forename: Michele
authors.initials: M
authors.lastname: Ceriotti
authors.forename: David E
authors.initials: DE
authors.lastname: Manolopoulos
authors.forename: Michele
authors.initials: M
authors.lastname: Parrinello
mesh_terms: D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water