NOVEL SCHEME TO STUDY STRUCTURAL AND THERMAL-PROPERTIES OF CONTINUOUSLY DEFORMABLE MOLECULES

In this article we present a method for calculating the chemical potential of arbitrary chain molecules in a computer simulation. The method is based on a generalization of Siepmann's method for calculating the chemical potential of chain molecules with a finite number of conformations. Next, we show that it is also possible to extend the configurational-bias Monte Carlo scheme developed recenty by Siepmann and Frenkel to continuously deformable molecules. The utility of our technique for computing the chemical potential of chain molecules is demonstrated by computing the chemical potential of a fully flexible chain consisting of 10-20 segments in a moderately dense atomic fluid. Under these conditions the conventional particle-insertion schemes fail completely. In addition, we show that our novel configurational-bias Monte Carlo scheme compares favourably with conventional Monte Carlo procedures for chain molecules.