Molecular alignment in molecular fluids induced by coupling between density and thermal gradients

CD Daub and J Tafjord and S Kjelstrup and D Bedeaux and F Bresme, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 18, 12213-12220 (2016).

DOI: 10.1039/c6cp01231k

We investigate, using non-equilibrium molecular dynamics simulations and theory, the response of molecular fluids confined in slit pores under the influence of a thermal gradient and/or an applied force. The applied force which has the same functional form as a gravitational force induces an inhomogeneous density in the confined fluid, which results in a net orientation of the molecules with respect to the direction of the force. The orientation is qualitatively similar to that induced by a thermal gradient. We find that the average degree of orientation is proportional to the density gradient of the fluid in the confined region and that the orientation increases with the magnitude of the force. The concurrent application of the external force and the thermal gradient allows us to disentangle the different mechanisms leading to the thermal orientation of molecular fluids. One mechanism is connected to the density variation of the fluid, while the second mechanism can be readily observed in molecular fluids consisting of molecules with mass or size asymmetry, even in the absence of a density gradient, hence it is connected to the application of the thermal gradient only.

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