Mass dipole contribution to the isotopic Soret effect in molecular mixtures

OR Gittus and F Bresme, JOURNAL OF CHEMICAL PHYSICS, 159, 114503 (2023).

DOI: 10.1063/5.0164253

Temperature gradients induce mass separation in mixtures in a process called thermal diffusion and are quantified by the Soret coefficient S-T. Thermal diffusion in fluid mixtures has been interpreted recently in terms of the so-called (pseudo-)isotopic Soret effect but only considering the mass and moment of inertia differences of the molecules. We demonstrate that the first moment of the molecular mass distribution, the mass dipole, contributes significantly to the isotopic Soret effect. To probe this physical effect, we investigate fluid mixtures consisting of rigid linear molecules that differ only by the first moment of their mass distributions. We demonstrate that such mixtures have non-zero Soret coefficients in contrast with S-T = 0 predicted by current formulations. For the isotopic mixtures investigated in this work, the dependence of S-T on the mass dipole arises mainly through the thermal diffusion coefficient D-T. In turn, D-T is correlated with the dependence of the molecular librational modes on the mass dipole. We examine the interplay of the mass dipole and the moment of inertia in defining the isotopic Soret effect and propose empirical equations that include the mass dipole contribution.

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