8.2.8. Long-range dispersion settings

The PPPM method computes interactions by splitting the pair potential into two parts, one of which is computed in a normal pairwise fashion, the so-called real-space part, and one of which is computed using the Fourier transform, the so called reciprocal-space or kspace part. For both parts, the potential is not computed exactly but is approximated. Thus, there is an error in both parts of the computation, the real-space and the kspace error. The just mentioned facts are true both for the PPPM for Coulomb as well as dispersion interactions. The deciding difference - and also the reason why the parameters for pppm/disp have to be selected with more care - is the impact of the errors on the results: The kspace error of the PPPM for Coulomb and dispersion interaction and the real-space error of the PPPM for Coulomb interaction have the character of noise. In contrast, the real-space error of the PPPM for dispersion has a clear physical interpretation: the underprediction of cohesion. As a consequence, the real-space error has a much stronger effect than the kspace error on simulation results for pppm/disp. Parameters must thus be chosen in a way that this error is much smaller than the kspace error.

When using pppm/disp and not making any specifications on the PPPM parameters via the kspace modify command, parameters will be tuned such that the real-space error and the kspace error are equal. This will result in simulations that are either inaccurate or slow, both of which is not desirable. For selecting parameters for the pppm/disp that provide fast and accurate simulations, there are two approaches, which both have their up- and downsides.

The first approach is to set desired real-space an kspace accuracies via the kspace_modify force/disp/real and kspace_modify force/disp/kspace commands. Note that the accuracies have to be specified in force units and are thus dependent on the chosen unit settings. For real units, 0.0001 and 0.002 seem to provide reasonable accurate and efficient computations for the real-space and kspace accuracies. 0.002 and 0.05 work well for most systems using lj units. PPPM parameters will be generated based on the desired accuracies. The upside of this approach is that it usually provides a good set of parameters and will work for both the kspace_modify diff ad and kspace_modify diff ik options. The downside of the method is that setting the PPPM parameters will take some time during the initialization of the simulation.

The second approach is to set the parameters for the pppm/disp explicitly using the kspace_modify mesh/disp, kspace_modify order/disp, and kspace_modify gewald/disp commands. This approach requires a more experienced user who understands well the impact of the choice of parameters on the simulation accuracy and performance. This approach provides a fast initialization of the simulation. However, it is sensitive to errors: A combination of parameters that will perform well for one system might result in far-from-optimal conditions for other simulations. For example, parameters that provide accurate and fast computations for all-atomistic force fields can provide insufficient accuracy or united-atomistic force fields (which is related to that the latter typically have larger dispersion coefficients).

To avoid inaccurate or inefficient simulations, the pppm/disp stops simulations with an error message if no action is taken to control the PPPM parameters. If the automatic parameter generation is desired and real-space and kspace accuracies are desired to be equal, this error message can be suppressed using the kspace_modify disp/auto yes command.

A reasonable approach that combines the upsides of both methods is to make the first run using the kspace_modify force/disp/real and kspace_modify force/disp/kspace commands, write down the PPPM parameters from the output, and specify these parameters using the second approach in subsequent runs (which have the same composition, force field, and approximately the same volume).

Concerning the performance of the pppm/disp there are two more things to consider. The first is that when using the pppm/disp, the cutoff parameter does no longer affect the accuracy of the simulation (subject to that gewald/disp is adjusted when changing the cutoff). The performance can thus be increased by examining different values for the cutoff parameter. A lower bound for the cutoff is only set by the truncation error of the repulsive term of pair potentials.

The second is that the mixing rule of the pair style has an impact on the computation time when using the pppm/disp. Fastest computations are achieved when using the geometric mixing rule. Using the arithmetic mixing rule substantially increases the computational cost. The computational overhead can be reduced using the kspace_modify mix/disp geom and kspace_modify splittol commands. The first command simply enforces geometric mixing of the dispersion coefficients in kspace computations. This introduces some error in the computations but will also significantly speed-up the simulations. The second keyword sets the accuracy with which the dispersion coefficients are approximated using a matrix factorization approach. This may result in better accuracy then using the first command, but will usually also not provide an equally good increase of efficiency.

Finally, pppm/disp can also be used when no mixing rules apply. This can be achieved using the kspace_modify mix/disp none command. Note that the code does not check automatically whether any mixing rule is fulfilled. If mixing rules do not apply, the user will have to specify this command explicitly.