Structure of Simple Dipolar Water-Like Fluids: Primitive Model and Hard Tetrahedra

Dipolar versions of two qualitatively different types of simple short range model fluids which exhibit the phenomenon of hydrogen bonding and which could thus serve as a reference in equations of state for associating fluids have been considered: the primitive model of water descending from the TIP4P model and the fluid of hard tetrahedra. The hydrogen bonding structure exhibited by the latter model results from purely repulsive interactions whereas in the first model the “hydrogen bonding interaction” is explicitly incorporated in the model. Since the water molecules bear a strong dipole moment, the effect of the added dipole-dipole interaction on the structure of the two short-range models is therefore examined considering them both in the full and screened dipole-dipole modifications. It is found that the hydrogen bonding structure in the primitive model resulting from the site-site interactions is so strong that the additional dipole-dipole interaction has only a marginal effect on its structure and contributes thus only to the internal energy. On the contrary, even only a weak dipole-dipole interaction destroys the original hydrogen bonding structure of the hard tetrahedron fluid; to preserve it, a screened dipole-dipole interaction has to be used in the equation of state development.

A simple second order thermodynamic perturbation theory for associating fluids

An approximation within Wertheim's second order perturbation theory is proposed which allows for the development of a general solution for pure component fluids with an arbitrary number and functionality of association sites. The solution is closed, concise and general for all second order effects such as ring formation, steric hindrance and hydrogen bond cooperativity. The approach is validated by comparison to hydrogen bond structure data for liquid water.