Noura Dawass

1 10 I NTRODUCTION N, V, T R 1 R 2 R 3 Figure 1.2: A schematic representation of the Small System Method (SSM) [16] , where thermo- dynamic properties are computed from the scaling of properties of small subvolumes with the inverse size of the subvolume. are difficult to extend to complex molecular systems. Recently, Krüger and co– workers [74] applied the Small System Method (SSM) [16] to develop a practical approach for computing KBIs from molecular simulation. This approach was derived for estimating KBIs of fluids, which is the focus of this thesis, and was ex- tended to solids as shown in the recent work of Miyaji et al. [77] . In the following subsection, the method of Krüger and co–workers [74] will be presented. After that, a summary of the other methods available in literature for computing KBIs frommolecular simulation is provided. T HE METHOD OF K RÜGER AND CO – WORKERS According to the SSM, properties of small subvolumes, that can be of the order of a few molecular diameters, are treated in terms of thermodynamics of small systems rather than classical thermodynamics [78] . According to Hill’s thermo- dynamics of small systems, properties of open embedded subvolumes scale with the inverse size of the subvolumes [78, 79] . This also applies to KBIs of finite sub- volumes, G V αβ [63, 74] . For a specific system, G V αβ computed from a number of subvolumes with different sizes, scale linearly with the inverse size of the sub- volume [63, 74, 80, 81] . See Figure 1.2 for an example of multiple subvolumes embedded in a simulation box.