Combining statistical-mechanical theories and neutron-scattering techniques, we show that the effective pair potential between star polymers is exponentially decaying for large distances and crosses over, at a density-dependent corona diameter, to an ultrasoft logarithmic repulsion for small distances. We also make the theoretical prediction that in concentrated star polymer solutions, this ultrasoft interaction induces an anomalous fluid structure factor which exhibits an unusually pronounced second peak.[S0031-9007(98)06148-1] PACS numbers: 61.25.Hq, 61.20.Gy, 82.70.Dd Star polymers consist of a well-defined number f of flexible polymer chains tethered to a central microscopic core. By enhancing this functionality (or arm number) f which governs the interpenetrability of two stars, one can continuously switch from unbranched polymer chains (f 1, 2) to a colloidal sphere (f ¿ 1). Hence, star polymers can actually be viewed as hybrids between polymerlike entities and colloidal particles establishing an important link between these different domains of physics. Moreover, star polymer solutions reveal quite a number of novel structural and dynamical properties which occur neither in single-chain polymers nor in suspensions of colloidal spheres; for recent reviews see Refs. [1,2].While the polymer conformations around a single star are well understood by computer simulation [3], scaling theory [4], and small-angle neutron scattering experiments [5], concentrated star polymer solutions are much more difficult to access due to the additional effective interactions between the stars. In particular, these interactions become relevant when the distance r between two star polymer centers is of the order of the so-called corona diameter s, which describes the spatial extension of the monomer density around a single star (see the inset of Fig. 1). This translates immediately into an overlap density r ء ϵ 1͞s 3 of the core number density r. Close to this overlap density r ء , there is an effective repulsion between stars resulting from the osmotic pressure arising between polymers from different cores. The repulsion is purely entropic; i.e., it simply scales with the thermal energy k B T . Witten and Pincus [6] were the first to derive the functional form of this repulsion. The effective potential between two stars, V ͑r͒, was found to depend logarithmically on r and to scale asymptotically as f 3͞2 with the arm number, i.e., V ͑r͒ 2k B T gf 3͞2 ln͑r͞s͒, where k B is Boltzmann's constant, T is the temperature, and g is an unknown numerical prefactor. Note that this result was obtained only for large f and for small distances r # s. Since this potential depends only weakly on r, the stars can be viewed as "ultrasoft" colloidal particles whose interaction is very different from common soft spheres described, e.g., by an inverse-power potential [7,8].The aim of this Letter is twofold: First, we describe the star polymer interaction quantitatively, proposing an explicit analytical expression for the effective pair potenti...
Recently, an increasing experimental effort has been devoted to the synthesis of complex colloidal particles with chemically or physically patterned surfaces and possible specific shapes that are far from spherical. These new colloidal particles with anisotropic interactions are commonly named patchy particles. In this Perspective article, we focus on patchy systems characterized by spherical neutral particles with patchy surfaces. We summarize most of the patchy particle models that have been developed so far and describe how their basic features are connected to the physical systems they are meant to investigate. Patchy models consider particles as hard or soft spheres carrying a finite and small number of attractive sites arranged in precise geometries on the particle's surface. The anisotropy of the interaction and the limited valence in bonding are the salient features determining the collective behavior of such systems. By tuning the number, the interaction parameters and the local arrangements of the patches, it is possible to investigate a wide range of physical phenomena, from different self-assembly processes of proteins, polymers and patchy colloids to the dynamical arrest of gel-like structures. We also draw attention to charged patchy systems: colloidal patchy particles as well as proteins are likely charged, hence the description of the presence of heterogeneously distributed charges on the particle surface is a promising perspective for future investigations.
We examine in full generality the phase behavior of systems whose constituent particles interact by means of potentials which do not diverge at the origin, are free of attractive parts and decay fast enough to zero as the interparticle separation r goes to infinity. By employing a mean fielddensity functional theory which is shown to become exact at high temperatures and/or densities, we establish a criterion which determines whether a given system will freeze at all temperatures or it will display reentrant melting and an upper freezing temperature.
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