The Debye’s model for the dielectric relaxation of liquid water and the role of cross-dipolar correlations. A MD-simulations study

Abstract

By means of massive (more than 1.2 · 106 molecules) molecular dynamics simulations at 300 K we have disentangled self- and cross-dipolar contributions to the dielectric relaxation of liquid water that cannot be experimentally resolved. We have demonstrated that cross dipolar correlations are of paramount importance. They amount for almost a 60% of the total dielectric amplitude. The corresponding relaxation function is a one-step Debye-like function with a characteristic time, τcross, of the order of the phenomenological Debye time, τD. In contrast, the relaxation function corresponding to the self-contribution is rather complex and contains a fast decay related to dipolar librations and a second relaxation step that can be well described by two exponentials: a low-amplitude fast process (τ0 = 0.31 ps) and a main slow process (τself = 5.4 ps) that fully randomizes the dipolar orientation. In addition to dipolar relaxation functions, we have also calculated scattering-like magnitudes characterizing translation and rotation of water molecules. Although these processes can be considered as “jump” processes in the short time range, at the time scale of about τD–τcross, at which the cross-dipolar correlations decay to zero, the observed behavior cannot be distinguished from that corresponding to uncoupled Brownian translational and rotational diffusion. We propose that this is the reason why the Debye model, which does not consider intermolecular dipolar interactions, seems to work at time t ≳ τD.