Molecular Dynamics Approach to Calculate the Thermodiffusion (Soret and Seebeck) Coefficients of Salts in Aqueous Solutions.

An approach to investigate the physical parameters related to ion thermodiffusion in aqueous solutions is proposed herein by calculating the equilibrium hydration free energy and the self-diffusion coefficient as a function of temperature, ranging from 293 to 353 K, using molecular dynamics simulations of infinitely diluted ions in aqueous solutions. Several ion force field parameters are used in the simulations, and new parameters are proposed for some ions to better describe their hydration free energy. Such a theoretical framework enables the calculation of some single-ion properties, such as heat of transport, Soret coefficient, and mass current density, as well as properties of salts, such as effective mass and thermal diffusion, Soret and Seebeck, coefficients. These calculated properties are compared with experimental data available from optical measurements and showed good agreement revealing an excellent theoretical predictability of salt thermodiffusion properties. Differences in single-ion Soret and self-diffusion coefficients of anions and cations give rise to a thermoelectric field, which affects the system response that is quantified by the Seebeck coefficient. The fast and slow Seebeck coefficients are calculated and discussed, resulting in values with mV/K order of magnitude, as observed in experiments involving several salts, such as KCl, NaCl, HCl, NaOH, TMAOH, and TBAOH. The present approach can be adopted for any ion or charged particle dispersed in water with the aim of predicting the thermoelectric field induced through the fluid. It has potential applications in designing electrolytes for ionic thermoelectric devices in order to harvest energy and thermoelectricity in biological nanofluids.