Water polarization induced by thermal gradients: the extended simple point charge model (SPC/E)

• Published in: The Journal of chemical physics 2013-07, Vol.139 (1), p.014504-014504
• Main Authors: Armstrong, J A, Bresme, F
• Format: Article
• Language: English
• Subjects: Computational fluid dynamics; Fluid flow; Fluids; Mathematical models; Point charge; Polarization; Statistical process control; Thermodynamics
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4811291

We investigate the non-equilibrium response of extended simple point charge (SPC/E) water to thermal gradients. Using non-equilibrium molecular dynamics simulations, we show that SPC/E water features the thermo-polarization orientation effect, namely, water becomes polarized as a response to a thermal gradient. The polarization field increases linearly with the thermal gradient, in agreement with predictions of non-equilibrium thermodynamics theory. This observation confirms the generality of the thermo-polarization effect, first reported using the Modified Central Force Model (MCFM), and shows this physical effect is present irrespective of the water model details, in particular, dipole moment magnitude and model flexibility. The magnitude of the effect is the same for both models, although the sign of the electrostatic field is reversed in going from the MCFM to the SPC/E model. We further analyze the impact that the molecular geometry and mass distribution has on the magnitude of the polarization. Our results indicate that the thermo-polarization effect should be observed in a wide range of polar fluids, including fluids where hydrogen bonding is not present. Using various molecular models, we show that the polarization of these fluids under appropriate thermodynamic conditions can be of the same order or stronger than in water.