Computing dielectric spectra in molecular dynamics simulations: using a cavity to disentangle self and cross correlations

Abstract: Dielectric spectra are typically obtained in molecular dynamics (MD) simulations by analyzing the fluctuations, in the absence of an applied electric field, of the total dipole moment of the simulation box. We compare this standard method with a protocol that focuses on a virtual cavity whose size is chosen to include short-range dipolar cross-correlations, while excluding long-range correlations that are affected by the choice of electrostatic boundary conditions. We tested this protocol on three non-polarizable systems with different dielectric permittivities. We showed that it produces the same dielectric spectra as the standard method while being less sensitive to noise. The question of the decomposition of a dielectric spectrum into self and cross contributions is discussed in the context of both methods. We propose that, for a liquid with a sufficiently high dielectric permittivity, the cavity protocol yields a self-spectrum consistent with the electrostatic boundary conditions applicable to the experimental situation.