Impact of higher order diagrams on phase equilibrium calculations for small molecules using lattice cluster theory

Patrick Zimmermann, Christoph Walowski, Sabine Enders

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The Lattice Cluster Theory (LCT) provides a powerful tool to predict thermodynamic properties of large molecules (e.g., polymers) of different molecular architectures. When the pure-component parameters of a certain compound have been derived by adjustment to experimental data and the number of atoms is held constant within the molecule so that only the architecture is changed, the LCT is capable of predicting the properties of isomers without further parameter adjustment just based on the incorporation of molecular architecture. Trying to predict the thermodynamic properties of smaller molecules, one might face some challenges, which are addressed in this contribution. After factoring out the mean field term of the partition function, the LCT poses an expression that involves corrections to the mean field depending on molecular architecture, resulting in the free energy formally being expressed as a double series expansion in lattice coordination number z and interaction energy ϵ. In the process of deriving all contributing sub-structures within a molecule, some parts have been neglected to this point due to the double series expansion being truncated after the order ϵ2z-2. We consider the neglected parts that are of the order z-3 and reformulate the expression for the free energy within the LCT to achieve a higher predictive capability of the theory when it comes to small isomers and compressible systems. The modified version was successfully applied for phase equilibrium calculations of binary mixtures composed of linear and branched alkanes.

Original languageEnglish
Article number094103
JournalJournal of Chemical Physics
Volume148
Issue number9
DOIs
Publication statusPublished - 7 Mar 2018

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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