Computing Thermodynamic and Transport Properties of Solutions using the Kirkwood-Buff Theory

The Kirkwood-Buff (KB) theory is useful for connecting microscopic behaviour with macroscopic properties including partial molar enthalpies, partial molar volumes, derivatives of activity coefficients, and compressibilities. Recently, a formulation to compute KB integrals from molecular simulations of finite, and closed systems was introduced. The KB integrals can be computed from density fluctuations in subvolumes embedded in larger reservoir, or from integrating radial distribution functions (RDFs). In this project, the capabilities and limitations of the new formulation are investigated.  For instance, we investigate size and shape effects related to the subvolumes. Eventually, enhancing the computation of the KB integrals will facilitate the computation of transport and thermodynamic properties of complex fluids using molecular simulations.   

Chair:
Engineering Thermodynamics

Involved People:
Noura Dawass
Thijs Vlugt

Facilities used: