The rich phase behavior of the thermopolarization of water: from a reversal in the polarization, to enhancement near criticality conditions

Abstract

We investigate using non-equilibrium molecular dynamics simulations the polarization of water induced by thermal gradients using the accurate TIP4P/2005 water model. The full dependence of the polarization covering a wide range of thermodynamic states, from near supercritical to ambient conditions, is reported. Our results show a strong dependence of the thermo-polarization field with the thermodynamic state. The field features a strong enhancement near the critical point, which can be rationalized in terms of the large increase and ultimately the divergence of the thermal expansion of the fluid at the critical temperature. We also show that the TIP4P/2005 model features a reversal in the sign of the thermal polarization at densities ∼1 g cm⁻³. The latter result is consistent with the recent observation of this reversal phenomenon in SPC/E water and points the existence of this general physical phenomenon in water.