Unification of Ewald and shifted force methods to calculate Coulomb interactions in molecular simulations.

Three new Ewald series are derived using a new strategy that does not start with a proposed charge spreading function. Of these, the Ewald series produced using shifted potential interactions for the Ewald real space series converges relatively slowly, while the corresponding expression using a shifted force (SF) interaction does not converge. A comparison is made between several approximations of the Ewald method and the SF route to include Coulomb interactions in molecular dynamics (MD) computer simulations. MD simulations of a model bulk molten salt and water were carried out. The recently derived α' variant of Ewald, by K. D. Hammonds and D. M. Heyes [J. Chem. Phys. 157, 074108 (2022)], has been developed analytically and found to be more accurate and computationally efficient than SF in part due to the smaller real space truncation distance that can be used. In addition, with α', the number of reciprocal lattice vectors required is reduced considerably compared with the standard Ewald implementations to give the same accuracy. The invention of the α' method shifts the computational balance back toward using an Ewald construction. The SF method shows greater errors in the Coulomb pressure and time dependent fluctuation properties compared to α'. It does not conserve the shadow Hamiltonian in a microcanonical MD simulation, whereas the α' method does, which facilitates long time stability and insignificant drift of properties over time. The speed of the Ewald computer code is improved by using a new lookup table method.

Optimization of the Ewald method for calculating Coulomb interactions in molecular simulations.

Practical implementations of the Ewald method used to compute Coulomb interactions in molecular dynamics simulations are hampered by the requirement to truncate its reciprocal space series. It is shown that this can be mitigated by representing the contributions from the neglected reciprocal lattice vector terms as a simple modification of the real space expression in which the real and reciprocal space series have slightly different charge spreading parameters. This procedure, called the α' method, enables significantly fewer reciprocal lattice vectors to be taken than is currently typical for Ewald, with negligible additional computational cost, which is validated on model systems representing different classes of charged system, a CsI crystal and melt, water, and a room temperature ionic liquid. A procedure for computing accurate energies and forces based on a periodic sampling of an additional number of reciprocal lattice vectors is also proposed and validated by the simulations. The convergence characteristics of expressions for the pressure based on the forces and the potential energy are compared, which is a useful assessment of the accuracy of the simulations in reproducing the Coulomb interaction. The techniques developed in this work can reduce significantly the total computer simulation times for medium sized charged systems, by factors of up to ∼5 for those in the classes studied here.

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

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.

Shadow Hamiltonian in classical NVE molecular dynamics simulations: A path to long time stability.

The shadow energy, Es, is the conserved quantity in microcanonical ensemble (NVE) molecular dynamics simulations carried out with the position Verlet central-difference algorithm. A new methodology for calculating precise and accurate values of Es is presented. It is shown for the first time that Es rather than E is constant during structural changes occurring within a supercooled liquid. It is also explained how to prepare and conduct microsecond range bulk-phase NVE simulations with essentially zero energy drift without the need for thermostating. The drift is analyzed with block averaging and new drift functions of the shadow energy. With such minimal drift, extremely small and accurate standard errors in the mean for quantities like Es, E, and temperature, T, can be obtained. Values of the standard error for Es of ≈10-10 in molecule-based reduced units can be routinely achieved for simulations of 108 time steps. This corresponds to a simulation temperature drift of ≈10-6 K/µs, six orders of magnitude smaller than generally considered to be acceptable for protein simulations. We also show for the first time how these treatments can be extended with no loss of accuracy to polyatomic systems with both flexible degrees of freedom and arbitrary geometric constraints imposed via the SHAKE algorithm. As a bonus, estimates of simulation-average kinetic and total energies from high order velocity expressions can be obtained to a good approximation from 2nd order velocities and the average mean square force (for polyatomics, this refers to per site, including any constraint forces).