Efficient and realistic simulation of phase coexistence

The Journal of Chemical Physics, vol. 153, pp. 244121

Abstract

We show how an existing concurrent multi-scale method named hybrid particle field-molecular dynamics (hPF-MD) can be adapted to enable the simulation of structure and/or structural dynamics in compressible systems. Implementing such new equations of state (EOS) into hPF-MD, while conserving the efficiency associated with treating intermolecular interactions in a continuum fashion, opens this method up to describe a new class of phenomena in which non-uniform densities play a role, for example, evaporation and crystallization. We carefully consider how compressible hPF-MD compares to its mean-field counterpart for two particular EOS, adopted from the Cell Model for polymers and the Carnahan-Starling expression for hard spheres. Here, we performed a very basic analysis for a single-component system, focusing on the significance of various particle-based parameters and the particle-to-field projection. Our results illustrate the key role of the particle density per field grid cell and show that projection based on a Gaussian kernel is preferred over the standard cloud-in-cell projection. They also suggest that the behavior of hPF-MD close to the critical point is non-classical, i.e., in agreement with a critical exponent for a pure particle description, despite the mean-field origin of the method.

Authors 4

1. G. J. A. Sevink corresponding Aachen Leiden Institute of Chemistry

   Yamagata University · Leiden University · University of Oslo

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University 1 , P.O. Box 9502, 2300 RA Leiden, The Netherlands

   Theoretical Physical Chemistry, Organic Materials Modeling, Department of Organic Materials Science, Yamagata University 2 , 4-3-16 Jonan, Yonezawa, Yamagata-ken 992-8510, Japan

   3Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, 0315, Oslo, Norway

2. Edgar M. Blokhuis Aachen Leiden Institute of Chemistry

   Yamagata University · Leiden University · University of Oslo

   Affiliation as printed

   Leiden Institute of Chemistry, Leiden University 1 , P.O. Box 9502, 2300 RA Leiden, The Netherlands

   Theoretical Physical Chemistry, Organic Materials Modeling, Department of Organic Materials Science, Yamagata University 2 , 4-3-16 Jonan, Yonezawa, Yamagata-ken 992-8510, Japan

   3Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, P.O. Box 1033 Blindern, 0315, Oslo, Norway

3. Xinmeng Li Aachen Leiden Institute of Chemistry

   Yamagata University · Leiden University · University of Oslo

   Affiliation as printed

   Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo 3 , P.O. Box 1033 Blindern, 0315, Oslo, Norway

   Leiden Institute of Chemistry, Leiden University 1 , P.O. Box 9502, 2300 RA Leiden, The Netherlands

   Theoretical Physical Chemistry, Organic Materials Modeling, Department of Organic Materials Science, Yamagata University 2 , 4-3-16 Jonan, Yonezawa, Yamagata-ken 992-8510, Japan

4. Giuseppe Milano Aachen

   Yamagata University · Leiden University · University of Oslo

   Affiliation as printed

   Department of Chemistry and Hylleraas Centre for Quantum Molecular Sciences, University of Oslo 3 , P.O. Box 1033 Blindern, 0315, Oslo, Norway

   Theoretical Physical Chemistry, Organic Materials Modeling, Department of Organic Materials Science, Yamagata University 2 , 4-3-16 Jonan, Yonezawa, Yamagata-ken 992-8510, Japan

   1Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands