Simulation of multiple ordered phases in C23 n-alkane

Nathaniel Wentzel, Scott T. Milner

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24 Scopus citations


Normal alkanes display multiple ordered phases, including an orthorhombic crystal (X) and two partially ordered rotator phases (RI and RII). The rotator phase transitions X-RI and RI-RII are of interest because they are weakly first-order, and because experiments suggest that crystalline polyethylene may nucleate via a metastable rotator phase. We have performed heating and cooling scans of all-atom NσT (isothermal, isostress) simulations of a pure C 23 solid. We find a sequence of phases, transition temperatures, structural and thermodynamic properties, all reasonably consistent with experiment, except that a monoclinic crystal is more stable in our simulations than the experimental orthorhombic structure. We find that the RI phase is well described as an orthorhombic crystal disordered by random ± 90 rotations of molecules about their stem axis, and the RII phase can be represented as a loose hexagonal packing of parallel chain stems, which tend to orient with the in-plane projection of C-C bonds pointing between neighbors. To measure local orthorhombic, RI, or RII order, we define Potts- and Ising-like order parameters, from which global order parameters and correlation functions can be computed. We observe modest pretransitional fluctuations of local RI order in the RII phase near TRI-RII, characteristic of this weakly first-order transition.

Original languageEnglish (US)
Article number224504
JournalJournal of Chemical Physics
Issue number22
StatePublished - Jun 14 2011

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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