Third virial coefficients and critical properties of quadrupolar two center Lennard-Jones models

Abstract

We report numerical results for the third virial coefficient of two center Lennard-Jones quadrupolar molecules. Calculations are performed for 35 models with different elongations and quadrupoles over a temperature range from half to twice the critical temperature. It is found that increasing the elongation at fixed quadrupole has the effect of increasing B3. On the other hand, at fixed elongation B3 first decreases with increasing quadrupole at low temperatures, then increases with increasing quadrupole at higher temperatures. We estimate the temperature at which the third virial coefficient vanishes. Although both this temperature and the critical temperature increase with the quadrupole moment, their ratio remains almost constant. We predict the critical properties using two different truncated virial series. The first one employs the exact second and third virial coefficients. The second one approximates the fourth order contribution by using estimates obtained for hard diatomics. It is found that both methods yield fairly good predictions, with a somewhat better performance of the approximate fourth order expansion. The two methods are complementary, however, because they consistently bracket the exact value as determined from computer simulations.