Liquid Water from First Principles: Investigation of Different Sampling Approaches

Abstract

A series of first principles molecular dynamics and Monte Carlo simulations were carried out for liquid water to investigate the reproducibility of different sampling approaches. These simulations include Car−Parrinello molecular dynamics simulations using the program cpmd with different values of the fictitious electron mass in the microcanonical and canonical ensembles, Born−Oppenheimer molecular dynamics using the programs cpmd and cp2k in the microcanonical ensemble, and Metropolis Monte Carlo using cp2k in the canonical ensemble. With the exception of one simulation for 128 water molecules, all other simulations were carried out for systems consisting of 64 molecules. Although the simulations yield somewhat fortuitous agreement in structural properties, analysis of other properties demonstrate that one should exercise caution when assuming the reproducibility of Car−Parrinello and Born−Oppenheimer molecular dynamics simulations for small system sizes in the microcanonical ensemble. In contrast, the m...