Shadow Hamiltonian in classical NVE molecular dynamics simulations involving Coulomb interactions.

Abstract

Microcanonical ensemble (NVE) Molecular Dynamics (MD) computer simulations are performed with negligible energy drift for systems incorporating Coulomb interactions and complex constraint schemes. In principle, such systems can now be simulated in the NVE ensemble for millisecond time scales, with no requirement for system thermostatting. Numerical tools for assessing drift in MD simulations are outlined, and drift rates of 10-6 K/μs are demonstrated for molten salts, polar liquids, and room temperature ionic liquids. Such drift rates are six orders of magnitude smaller than those typically quoted in the literature. To achieve this, the standard Ewald method is slightly modified so the first four derivatives of the real space terms go smoothly to zero at the truncation distance, rc. New methods for determining standard Ewald errors and the new perturbation errors introduced by the smoothing procedure are developed and applied, these taking charge correlation effects explicitly into account. The shadow Hamiltonian, Es, is shown to be the strictly conserved quantity in these systems, and standard errors in the mean of one part in 1010 are routinely calculated. Expressions for the shadow Hamiltonian are improved over previous work by accounting for O(h4) terms, where h is the MD time step. These improvements are demonstrated by means of extreme out-of-equilibrium simulations. Using the new methodology, the very low diffusion coefficients of room temperature 1-hexyl-3-methyl-imidazolium chloride are determined from long NVE trajectories in which the equations of motion are known to be integrated correctly, with negligible drift.