Noura Dawass

A PPLICATIONS OF K IRKWOOD –B UFF I NTEGRALS 1 19 In Refs. [72, 73, 94] , it was shown that KBIs can be used to correct finite-size effects of computed MS diffusion coefficients. MS diffusion coefficients depend on the size of the simulated system. These finite-size effects originate from hy- drodynamic interactions [72, 95, 96] . In the studies by Jamali et al. [72, 94] , a correction based on viscosity and the thermodynamic factor was used to com- pensate for this effect. For binary and ternary systems, KBIs were obtained from molecular simulation and used to compute thermodynamic factors. The finite- size correction was validated for various molecular systems such as organic flu- ids. Jamali et al. [72, 94] found the finite-size effects of MS diffusivites to be sig- nificant, especially when mixtures are close to demixing, or when molecules are large compared to the size of the simulation box [97, 98] . 1.4.4. O THER APPLICATIONS In section 1.1, we presented the relations that link KBIs to partial derivatives of the chemical potential with respect to the number of molecules (Eq. (1.5) ), partial molar volumes (Eq. (1.6) ), and isothermal compressibilities (Eq. (1.7) ) for binary systems. Based on these relations, other properties can be estimated from KBIs. Galata et al. [54] used the KB theory to compute thermodynamic mixing properties and excess properties of liquid mixtures. In their work, the authors focus on computing partial derivatives of the chemical potential with composi- tion and the Gibbs energy of mixing, ∆ mix G , which are important quantities for the prediction of phase equilibria of liquid mixtures. The prediction of ∆ mix G and other mixing properties from KBIs was validated using binary ideal and real LJ mixtures [54] . The KBIs were found using simulations of finite volumes, and finite-size effects were corrected using the approach of Cortes-Huerto et al. [83] . KBIs can be used to interpret findings from simulations of biological molecules. In Ref. [99] , Pierce et al. presented a review of the applications of the KB theory to biological systems. One of the valuable applications of the KB theory is to study the effects of co–solvents on biomolecules. Molecular simu- lation provide local information on the co–solvents surrounding biomolecules and how such an environment affects the structure of biomolecules [99– 103] . In 2004, Smith [102] demonstrated how KBIs can be used to relate simulation results, which provide preferential interaction, to macroscopic thermodynamic data [104] . Other than studying solvents surrounding biomolecules, the KB the- ory can be applied directly to systems with interacting biomolecules. However, this application can be hindered by difficulties associated with sampling the phase space of such systems.