Microscopic mechanism of thermomolecular orientation and polarization

Recent molecular dynamics simulations show that thermal gradients can induce electric fields in water that are comparable in magnitude to electric fields seen in ionic thin films and biomembranes. This surprising non-equilibrium phenomenon of thermomolecular orientation is also observed more generally in simulations of polar and non-polar size-asymmetric dumbbell fluids. However, a microscopic theory linking thermomolecular orientation and polarization to molecular properties is yet unknown. Here, we formulate an analytically solvable microscopic model of size-asymmetric dumbbell molecules in a temperature gradient using a mean-field, local equilibrium approach. Our theory reveals the relationship between the extent of thermomolecular orientation and polarization, and molecular volume, size anisotropy and dipole moment. Predictions of the theory agree quantitatively with molecular dynamics simulations. Crucially, our framework shows how thermomolecular orientation can be controlled and maximized by tuning microscopic molecular properties.