Noura Dawass

C ONTENTS 1 Introduction 1 1.1 The Kirkwood-Buff theory . . . . . . . . . . . . . . . . . . . . . . . . 3 1.2 Inversion of the Kirkwood–Buff theory . . . . . . . . . . . . . . . . . 6 1.3 Kirkwood–Buff Integrals frommolecular simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 1.3.1 Thermodynamic properties frommolecular simulations . . . 8 1.3.2 Methods for computing Kirkwood–Buff Integrals . . . . . . . 9 1.4 Applications of Kirkwood–Buff Integrals computed frommolecular simulation . . . . . . . . . . . . . . . . . 16 1.4.1 Partial molar enthalpies . . . . . . . . . . . . . . . . . . . . . 16 1.4.2 Properties of single-ions in salt solutions . . . . . . . . . . . . 16 1.4.3 Mass transfer in multicomponent liquids . . . . . . . . . . . 17 1.4.4 Other applications . . . . . . . . . . . . . . . . . . . . . . . . 19 1.5 Scope of this thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 2 Shape Effects of Kirkwood–Buff Integrals of Finite Systems 23 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.2 Numerical computation of w ( x ) . . . . . . . . . . . . . . . . . . . . 25 2.2.1 Importance sampling algorithm for computing p ( i ). . . . . . 27 2.2.2 Computing w ( x ) . . . . . . . . . . . . . . . . . . . . . . . . . 28 2.3 Shape effects of Kirkwood–Buff Integrals . . . . . . . . . . . . . . . . 28 2.3.1 The functions w ( x ) for a cube, cuboids, and spheroids . . . . 28 2.3.2 Kirkwood–Buff Integrals for various shapes . . . . . . . . . . 32 2.4 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 3 Finite-Size Effects of Kirkwood–Buff Integrals from Molecular Simu- lations 39 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40 3.2 Finite-size effects of subvolumes . . . . . . . . . . . . . . . . . . . . 41 3.3 Finite-size effects of radial distribution functions . . . . . . . . . . . 42 3.3.1 Van der Vegt correction. . . . . . . . . . . . . . . . . . . . . . 43 3.3.2 Inverse- N finite-size correction . . . . . . . . . . . . . . . . . 44 3.3.3 Cortes-Huerto et al. correction . . . . . . . . . . . . . . . . . 44 3.3.4 Simulation details . . . . . . . . . . . . . . . . . . . . . . . . 46 vii