Simulating dielectric spectra: A demonstration of the direct electric field method and a new model for the nonlinear dielectric response

We demonstrate a method to compute the dielectric spectra of fluids in molecular dynamics (MD) by directly applying electric fields to the simulation. We obtain spectra from MD simulations with low magnitude electric fields (approximate to 0.01 V/angstrom) in agreement with spectra from the fluctuation-dissipation method for water and acetonitrile. We examine this method's trade-off between noise at low field magnitudes and the nonlinearity of the response at higher field magnitudes. We then apply the Booth equation to describe the nonlinear response of both fluids at low frequency (0.1 GHz) and high field magnitude (up to 0.5 V/angstrom). We develop a model of the frequency-dependent nonlinear response by combining the Booth description of the static nonlinear dielectric response of fluids with the frequency-dependent linear dielectric response of the Debye model. We find good agreement between our model and the MD simulations of the nonlinear dielectric response for both acetonitrile and water.

Automated summary

We present a method for computing the dielectric spectra of fluids in molecular dynamics (MD) simulations by directly applying electric fields. We obtain spectra from MD simulations with low magnitude electric fields (approximately 0.01 V/angstrom) that agree with spectra from the fluctuation-dissipation method for water and acetonitrile. We investigate the trade-off between noise and nonlinearity in the response of fluids at different field magnitudes.