the use of top-down methodologies of this type are however surprisingly rare. The philosophy of coupling the development of intermolecular parameters from an accurate algebraic theory with molecular simulation was employed early on by Müller and Gubbins who used a high-fidelity semi-empirical representation of the LJ fluid together with dipolar and associative contributions combined as an EoS of the SAFT form to obtain a model for water. The adequacy of the approach is limited only by the deteriorating accuracy of the theory for low-temperature, high-density states and in the neighborhood of the critical region. In a similar fashion, Cuadros et al. employed an engineering EoS for the LJ fluid to regress from it molecular parameters for isotropic fluids. Ben-Amotz et al. also discuss the direct use of the LJ EoS to obtain corresponding states parameters for the underlying intermolecular potential. In a similar vein, Vrabec et al.,,, have championed the use of EoS to aid in the fitting of models for fluids of industrial interest. These are based on intermolecular potentials for 2-center LJ models with added dipoles and quadrupoles. These latter approaches, however, are restricted to the use of a LJ potential and suffer from a lack of flexibility as compared to the Mie potential. For a more complete discussion on the most recent schemes used to combined EoS to simulations the reader is referred to a review by Muller and Jackson. 4. Corresponding states parametrization We consider molecules composed of tangent spheres, where no restriction is placed m on the bonding angle between spheres (a pearl-necklace model). We take here six cases, = 1, 2, 3, 4, 5 and 6; although no element in the theory limits the value of m m.
the use of top-down methodologies of this type are however surprisingly rare. The philosophy of coupling the development of intermolecular parameters from an accurate algebraic theory with molecular simulation was employed early on by Müller and Gubbins who used a high-fidelity semi-empirical representation of the LJ fluid together with dipolar and associative contributions combined as an EoS of the SAFT form to obtain a model for water. The adequacy of the approach is limited only by the deteriorating accuracy of the theory for low-temperature, high-density states and in the neighborhood of the critical region. In a similar fashion, Cuadros et al. employed an engineering EoS for the LJ fluid to regress from it molecular parameters for isotropic fluids. Ben-Amotz et al. also discuss the direct use of the LJ EoS to obtain corresponding states parameters for the underlying intermolecular potential. In a similar vein, Vrabec et al.,,, have championed the use of EoS to aid in the fitting of models for fluids of industrial interest. These are based on intermolecular potentials for 2-center LJ models with added dipoles and quadrupoles. These latter approaches, however, are restricted to the use of a LJ potential and suffer from a lack of flexibility as compared to the Mie potential. For a more complete discussion on the most recent schemes used to combined EoS to simulations the reader is referred to a review by Muller and Jackson. 4. Corresponding states parametrization We consider molecules composed of m tangent spheres, where no restriction is placed on the bonding angle between spheres (a pearl-necklace model). We take here six cases, m = 1, 2, 3, 4, 5 and 6; although no element in the theory limits the value of m.