Phase Behavior of a Family of Truncated Hard Cubes Anjan P

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Phase Behavior of a Family of Truncated Hard Cubes Anjan P THE JOURNAL OF CHEMICAL PHYSICS 142, 054904 (2015) Phase behavior of a family of truncated hard cubes Anjan P. Gantapara,1,a) Joost de Graaf,2 René van Roij,3 and Marjolein Dijkstra1,b) 1Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands 2Institute for Computational Physics, Universität Stuttgart, Allmandring 3, 70569 Stuttgart, Germany 3Institute for Theoretical Physics, Utrecht University, Leuvenlaan 4, 3584 CE Utrecht, The Netherlands (Received 8 December 2014; accepted 5 January 2015; published online 5 February 2015; corrected 9 February 2015) In continuation of our work in Gantapara et al., [Phys. Rev. Lett. 111, 015501 (2013)], we inves- tigate here the thermodynamic phase behavior of a family of truncated hard cubes, for which the shape evolves smoothly from a cube via a cuboctahedron to an octahedron. We used Monte Carlo simulations and free-energy calculations to establish the full phase diagram. This phase diagram exhibits a remarkable richness in crystal and mesophase structures, depending sensitively on the precise particle shape. In addition, we examined in detail the nature of the plastic crystal (rotator) phases that appear for intermediate densities and levels of truncation. Our results allow us to probe the relation between phase behavior and building-block shape and to further the understanding of rotator phases. Furthermore, the phase diagram presented here should prove instrumental for guiding future experimental studies on similarly shaped nanoparticles and the creation of new materials. C 2015 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4906753] I. INTRODUCTION pressures, i.e., at densities below close packing. Some of the first examples of the importance of studying larger (non- Material design based on nanoparticle assemblies have crystalline) assemblies appeared, when it was discovered been at the focus of materials science over the past that there exists a tetrahedron packing into a quasicrystal decade. In particular, the self-assembly of polyhedral colloidal arrangement with close-packed density much higher than nanoparticles into functional materials with targeted properties that of spheres.21,24–26 Simultaneously, the phase diagrams has attracted huge interest. Recent advances in experimental for hard superballs,27,28 a family of truncated tetrahedra,29 techniques led to the synthesis of a wide variety of polyhedron- and a family of truncated cubes30 were established. The shaped particles, such as cubes,1–4 truncated cubes,1,5–7 importance of mesophase structures was further underpinned truncated octahedra,5,8 octahedra,5 tetrahedra,9 superballs,10 by investigations of space filling polyhedra,31 truncated and rhombic dodecahedra.11,12 In addition to controlled cubes32 and bifrustums33 at an interface, and a large number synthesis, the ability to perform self-assembly experiments of polyhedral particles.34 with these polyhedral particles5,10,13–18 has made significant To date, only one experimental investigation of a family strides forward. of truncated particles has been undertaken. Using a polyol This motivated many physicists, mathematicians, and synthesis technique, Henzie et al.5 reported the shape- computer scientists to investigate and try to classify the close- controlled synthesis of monodisperse silver (Ag) nanocrystals packed structures exhibited by these particles. Initially, the including cubes, truncated cubes, cuboctahedra, truncated focus lay on the prediction of the maximum crystalline packing octahedra, and octahedra. They used these polyhedral particles for faceted particles, as these structures are likely to form to study the close-packed crystal structures via sedimentation upon deposition and evaporation, and also have interesting experiments and simulations. Henzie et al. created exotic geometric properties.19–21 Recent extensive investigations of superlattices with potential applications in nanophotonics, many particle shapes demonstrated the importance of shape photocatalysis, and plasmonics. Their results tested several for the high-density (close-packed) structures. In particular, de conjectures on the densest packings of hard polyhedra.19–21,35 Graaf et al.22 investigated the closed packed structures of 142 In addition to the close-packed structure studies in the bulk, convex polyhedra, as well as 17 nonconvex faceted shapes. they also investigated the influence of walls on the sedimented More recently, Chen et al.23 considered over 55 000 convex structures. shapes, using theoretical, numerical, and computational However, Henzie et al. did not examine the finite-pressure methods. behavior of the system. At finite pressures, the structures Advances in computer power and performance have made that form by self-assembly may differ substantially from it possible to perform simulations of these systems with large the packings achieved at high (sedimentation and solvent- numbers of particles and opened up the way for a thorough evaporation) pressures. For instance, simulations of superballs examination of the phase behavior of faceted colloids at finite and of truncated cubes exhibited plastic-crystal phases,28,30,31 while cubes, cuboids, and truncated cubes exhibit vacancy- 30,36,37 a)Electronic mail: [email protected] rich simple cubic and tetrahedra exhibit quasicrystalline b)Electronic mail: [email protected] mesophases.29 In fact, for almost all truncated particle shapes 0021-9606/2015/142(5)/054904/16/$30.00 142, 054904-1 © 2015 AIP Publishing LLC 054904-2 Gantapara et al. J. Chem. Phys. 142, 054904 (2015) studied thus far, the finite-pressure phases and those formed IV B, followed by a discussion of the full phase diagram in under close-packed conditions differ substantially.34 Sec.IVE. In Sec.IVF, we analyze the orientation distributions In this manuscript, we investigate the finite-pressure of particles in the various plastic-crystal phases observed in behavior of particles similar to those considered by Henzie the phase diagram. Finally, we discuss the results and draw et al. Here, we present a thorough investigation of the conclusions in Sec.V. phase behavior of a family of truncated hard cubes, which interpolates smoothly between cubes and octahedra (the mathematical dual of the cube) via cuboctahedra. We describe II. SIMULATION MODEL in detail the different phases, as well as the nature of the phase The particles that we investigated are completely specified transitions between these phases. This work is an extension by the level of truncation of a perfect cube, which we denote by of our previous investigation of these systems, see Ref. 30, s 2 0;1 , and the volume of the particle. We define our family and makes several minor updates on our previous results. In of truncated[ ] cubes using a simple mathematical expression the present paper, we put additional emphasis on the analysis for the location of the vertices. The line segments that connect of the plastic crystal or rotator phases and the computational these vertices can only be assigned in one (unique) way to details. obtain a truncated cube. The vertices of a truncated cube may We used Monte Carlo (MC) simulation studies and free- be written as a function of the shape parameter s 2 0; 1 : energy calculations to establish the phase diagram for this [ ] ! −1=3 ! !T system. This diagram exhibits a remarkably rich diversity 4 ( ) 1 1 1 1− s3 P ± − s ;± ;± in crystal structures that show a sensitive dependence on 3 D 2 2 2 the particle shape. Changes in phase behavior and crystal >8 1 > s 2 0; structures occur even for small variations in the level of > " 2 # v s = > ; (1) truncation. This is an unexpected result, since the particle > ! −1=3 { ( )} > 4 ( ) shape varies smoothly from that of a cube to that of an > −4λ3 P ± 1− λ ; ±λ; 0 T < 3 D octahedron by truncation. We also observed that for specific > ( ( ) ) > 1 levels of truncation, the particles possess an equation of state > λ ≡ 1− s 2 0; > " 2 # (EOS) that exhibits three distinct crystal phases as well as an > > isotropic fluid phase. where PD is: a permutation operation that generates all In addition, we found that for close-to-cubic particles that permutations of each element in the sets of 8 and 4 vertices form a vacancy-rich simple cubic (SC) phase, the equilibrium spanned by the ±-operations, respectively. The duplicate concentration of vacancies increases at a fixed packing fraction vertices that are a consequence of this definition are removed 30 φ upon increasing the level of truncation, see Gantapara et al. after letting PD act. The “T” indicates transposition. The The vacancy concentrations for truncated cubes for small prefactors ensure that the truncated cubes are normalized truncations are in agreement with the vacancy concentration to unit volume. Several Platonic and Archimedeanp solids of perfect cubes.36 However, our results differ from those are members of this family: s = 0 a cube, s = 2 − 2 =2 obtained by Monte Carlo simulations for parallel cuboids, ≈ 0:292 893 a truncated cube, s = 1=2 a cuboctahedron,( s = 2)=3 where the vacancy concentration remains constant, when the a truncated octahedron, and s = 1 an octahedron; these are shape is varied from a perfect cube to a sphere via rounded depicted in Fig. 1(a). cubes (so-called cuboids).37 Furthermore, we analyzed the orientation distribution properties of particles in the plastic-crystal phases observed III. SIMULATION METHODS in the truncated cubes phase diagram. The orientation A. Order parameters and correlations functions distribution function of plastic crystals of hard anisotropic particles is shown to be highly anisotropic and strongly peaked In this subsection, we describe different order parameters for specific orientations. Based on our results, we present that we used to quantify the positional and orientation order of a grouping of particles with different asphericity A values particles in our isothermal-isobaric Monte Carlo simulations according to their cubatic order S4 near (plastic-)crystal-fluid (also called NPT simulations; fixed pressure P, temperature transition regions. We find that particles with asphericity T, and number of particles N) of the truncated cubes.
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