Are dipolar liquids ferroelectric? Simulation studies

The observation of a very sharp low frequency spike in the hyper-Rayleigh spectrum (HRS) of strongly dipolar fluids, such as acetonitrile and water, has been interpreted as reflecting a very slowly relaxing component in the transverse dipole density. This suggestion is at variance with the expectation of the dielectric theory for an isotropic fluid and has led to the speculation that the slow relaxation is associated with the reorganization of ferroelectric domains. Very large-scale molecular-dynamics simulation (approximately 28,000 molecules) have been carried out using a three-site potential model of acetonitrile. The simulated fluid shows no suggestion of strong dipole correlations and domain structure. The dipole density correlations behave as predicted by the normal dielectric theory and their spectra do not show the low-frequency feature seen in the HRS. In order to examine the characteristics of the spectra which would be seen in a ferroelectric domain, the acetontrile model was transmuted to more closely resemble a Stockmayer-type fluid with the same dipole density and a ferroelectric phase was observed. In this phase the dielectric spectra show (i) a high-frequency spectral feature due to librational motion of the molecules within a domain, and (ii) slowly-relaxing longitudinal and transverse polar modes, again at variance from the experimental HRS characteristics.