Physical mechanisms of the Soret effect in binary Lennard-Jones liquids elucidated with thermal-response calculations

The Soret effect is the tendency of fluid mixtures to exhibit concentration gradients in the presence of a temperature gradient. Using molecular-dynamics simulation of two-component Lennard-Jones liquids, it is demonstrated that spatially sinusoidal heat pulses generate both temperature and pressure gradients. Over short timescales, the dominant effect is the generation of compressional waves, which dissipate over time as the system approaches mechanical equilibrium. The approach to mechanical equilibrium is also characterized by a decrease in particle density in the high-temperature region and an increase in particle density in the low-temperature region. It is demonstrated that concentration gradients develop rapidly during the propagation of compressional waves through the liquid. Over longer timescales, heat conduction occurs to return the system to thermal equilibrium, with the particle current acting to restore a more uniform particle density. It is shown that the Soret effect arises due to the fact that the two components of the fluid exhibit different responses to pressure gradients. First, the so-called isotope effect occurs because light atoms tend to respond more rapidly to evolving conditions. In this case, there appears to be a connection to previous observations of "fast sound" in binary fluids. Second, it is shown that the partial pressures of the two components in equilibrium, and more directly, the relative magnitudes of their derivatives with respect to temperature and density, determine which species accumulate in the high- and low-temperature regions. In the conditions simulated here, the dependence of the partial pressure on density gradients is larger than the dependence on temperature gradients. This is directly connected to the accumulation of the species with the largest partial pressure in the high-temperature region and the accumulation of the species with the smallest partial pressure in the low-temperature region. The results suggest that further development of theoretical descriptions of the Soret effect might begin with hydrodynamical equations in two-component liquids. Finally, it is suggested that the recently proposed concept of "thermophobicity" may be related to the sensitivity of partial pressures in a multicomponent fluid to changes in temperature and density.