Dual chain perturbation theory: A new equation of state for polyatomic molecules

• Published in: The Journal of chemical physics Vol. 144; no. 16; pp. 164104 - 164113
• Main Author: Marshall, Bennett D.
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 28.04.2016
• Subjects: Chains; CLUSTER EXPANSION; Clusters; CORRELATION FUNCTIONS; DISTURBANCES; EQUATIONS OF STATE; EXPERIMENTAL DATA; FREE ENERGY; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Mathematical analysis; MATHEMATICAL METHODS AND COMPUTING; MOLECULES; PERTURBATION THEORY; Physics; Polyatomic molecules; Reference systems
• ISSN: 0021-9606; 1089-7690; 1089-7690
• DOI: 10.1063/1.4947023

In the development of equations of state for polyatomic molecules, thermodynamic perturbation theory (TPT) is widely used to calculate the change in free energy due to chain formation. TPT is a simplification of a more general and exact multi-density cluster expansion for associating fluids. In TPT, all contributions to the cluster expansion which contain chain–chain interactions are neglected. That is, all inter-chain interactions are treated at the reference fluid level. This allows for the summation of the cluster theory in terms of reference system correlation functions only. The resulting theory has been shown to be accurate and has been widely employed as the basis of many engineering equations of state. While highly successful, TPT has many handicaps which result from the neglect of chain–chain contributions. The subject of this document is to move beyond the limitations of TPT and include chain–chain contributions to the equation of state.