The liquid structure of tetrachloroethene: Molecular Dynamics simulations and Reverse Monte Carlo modeling with interatomic potentials

Gereben, Orsolya and Pusztai, László (2013) The liquid structure of tetrachloroethene: Molecular Dynamics simulations and Reverse Monte Carlo modeling with interatomic potentials. JOURNAL OF CHEMICAL PHYSICS, 139. pp. 1-32. ISSN 0021-9606

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Abstract

The liquid structure of tetrachloroethene has been investigated on the basis of measured neutron and X-ray scattering structure factors, applying molecular dynamics simulations and reverse Monte Carlo (RMC) modeling with flexible molecules and interatomic potentials. As no complete all-atom force field parameter set could be found for this planar molecule, the closest matching OPLS-AA intra-molecular parameter set was improved by equilibrium bond length and angle parameters coming from electron diffraction experiments [Karle, I. L.; Karle, J. J. Chem. Phys. 1952, 20 63]. In addition, four different intra-molecular charge distribution sets were tried, so in total, eight different molecular dynamics simulations were performed. The best parameter set was selected by calculating the mean square difference between the calculated total structure 1 factors and the corresponding experimental data. The best parameter set proved to be the one that uses the electron diffraction based intra-molecular parameters and the charges qC=0.1 and qCl =–0.05. The structure was further successfully refined by applying RMC computer modeling with flexible molecules that were kept together by interatomic potentials. Correlation functions concerning the orientation of molecular axes and planes were also determined. They reveal that the molecules closest to each other exclusively prefer the parallel orientation of both the molecular axes and planes. Molecules forming the first maximum of the center-center distribution have a preference for <30 º and >60 º axis orientation and >60 º molecular plane arrangement. A second coordination sphere at ~11 Å and a very small third one at ~16 Å can be found as well, without preference for any axis or plane orientation.

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