A single-site pair potential is derived to approximate the linear n -site square well interaction. The resulting square well line (SWL) potential is analytical, fairly smooth, and reproduces the distance and orientation dependence of the multisite pair energy. It contains only three control parameters n, L, and s2, in addition to the units of length s 1 and energy ε. The advantages of the new model over the traditional potentials such as Gay-Berne and Kihara are that n, L, and s 2 are physically meaningful quantities and that no additional adjustable parameters are introduced. With the SWL potential even very long square well chain molecules may be treated in Monte Carlo (MC) simulations; moreover the model is well suited for perturbation theory. Using Onsager-like theories we test the effect of molecular elongation, temperature, and the range of the square well potential on the vapor-liquid and nematic-smectic A (NS) phase transitions. We find that the vapor-liquid binodal of the SWL fluid is in good agreement with MC results for square well dumbbells. For repulsive SWL particles, varying the interaction range s2 results in a similar effect on the NS transition as the change in the ionic strength in a real suspension of fd viruses.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry