Novel scheme to study structural and thermal properties of continuously deformable molecules

Abstract

In this anicle we present a method for alculating the chemical potential of arbitrary chain molecules in a mmpuier simulation. The method is based on a generalization of Siepmann's method tor mlculaling the chemical potential of chain molecules with a finite number of conformations. Next. we show that it is also possible 10 atend the configurational-bias Monte Carlo scheme developed recenty by Siepmann and Frenkel to continuously deformable molecules. ?he utility of our technique for computing the chemical potenlial of chain molecules is demonstrated ty computing the chemical potential of a fully flexible chain mnsisting of 10-20 segments in a moderately dense atomic fluid. Under these mnditions the conventional particle.inserlion schemes [ail mmpletely. In addition, we show hat our novel configuralional-bias Monre Carlo scheme ampam favourably vlith conventional Monte Carlo procedures for chain molecules.