We present a comparative assessment of the performance of the M06 suite of density functionals (M06, M06-2X, and M06-HF) against an MP2 benchmark for calculating the relative energies and geometric structures of the Cl(-)·arginine and Br(-)·arginine halide ion-amino acid clusters. Additional results are presented for the popular B3LYP density functional. The Cl(-)·arginine and Br(-)·arginine complexes are important prototypes for the phenomenon of anion-induced zwitterion formation. Results are presented for the canonical (noncharge separated) and zwitterionic (charge separated) tautomers of the clusters, as well as the numerous conformational isomers of the clusters. We find that all of the M06 functions perform well in terms of predicting the general trends in the conformer relative energies and identifying the global minimum conformer. This is in contrast to the B3LYP functional, which performed significantly less well for the canonical tautomers of the clusters where dispersion interactions contribute more significantly to the conformer energetics. We find that the M06 functional gave the lowest mean unsigned error for the relative energies of the canonical conformers (2.10 and 2.36 kJ/mol for Br(-)·arginine and Cl(-)·arginine), while M06-2X gave the lowest mean unsigned error for the zwitterionic conformers (0.85 and 1.23 kJ/mol for Br(-)·arginine and Cl(-)·arginine), thus providing insight into the types of physical systems where each of these functionals should perform best.

of the original manuscript:Ungar, G.; Tschierske, C.; Abetz, V.; Holyst, R.; Bates, M.A.; Lui, F.; Prehm, M.; Kieffer, R.; Zeng, X.; Walker, M.; Glettner, B.; Zywocinski, A.: Keywords: columnar liquid crystals, polygonal honeycombs, polyphiles, miktoarm star terpolymers, simulation, Langmuir films, rod-coil molecules, surface alignment Abstract: This article reviews the diversity of phase morphologies observed recently in starbranched liquid crystalline and polymeric compounds containing at least three immiscible segments. Bolaamphiphiles and facial amphiphiles with a rod-like aromatic core, two endgroups and one (T-shape) or two chains (X-shape) attached laterally to the core form numerous honeycomb-like liquid crystal phases, as well as a variety of novel lamellar and 3D-ordered mesophases. Molecular self-organization is described in bulk phases and in thin films on solid and liquid surfaces, as well as in Langmuir-Blodgett films. The remarkably reversible formation of mono-and tri-layer films is highlighted. In the bulk, T-shaped "rod-coil" molecules without the appended end-groups form predominantly lamellar phases if the core is a straight rod, but the bent-core variety forms hexagonal honeycombs. Furthermore, selfassembly of "Janus"-type molecules, such as those with Y-shaped star mesogens bearing different mutually incompatible side-groups, is discussed. Also covered is the diversity of morphologies observed in miktoarm star terpolymers i.e. polymers with three different and 3 incompatible arms of well-defined lengths. A range of bulk phases with 3D or 2D order are observed, combining layers, cylinders and cocontinuous networks. Similarities and differences are highlighted between the liquid crystal morphologies on the 3-15 nm scale and the polymer morphologies on the scale 10-100 nm. A separate section is dedicated to computer simulations of such systems, particularly those using dissipative particle and molecular dynamics. Of special interest are the recently synthesised X-shaped tetraphilic molecules, where two different and incompatible side-chains are attached at opposite sides of the rod-like core. The tendency for their phase separation produces LC honeycombs with cells of different compositions that can be represented as paving a plane with different color tiles. Self-Assembly at Different Length Scales: Polyphilic StarBranched Liquid Crystals and Miktoarm Star CopolymersThe independent variation of chain length and "color" creates the potential for developing a considerable range of complex new 2d-and 3d soft nanostructures. Analogous X-shaped rodcoil compounds with unequal side groups are also of considerable interest, forming tubular lyotropic structures capable of confining strings of guest molecules.

Gelation by small molecules is enormously topical in catalysis, nanomaterials, drug delivery, and pharmaceutical crystallization. The way in which gelators selforganize to give a 3D gel network is poorly understood. How does a system progress from a continuous pattern of supramolecular motifs to a network of fibers with well-defined morphologies? Why are gel fibers so homogeneous, and why do they form instead of crystals? This work shows, predictively, that gels arise by the scrolling of sheets with asymmetric surface structures.

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No place like kagome: A quaternary amphiphile displays a novel complex liquid‐crystalline phase formed by a periodic array combining triangular and hexagonal cylinders, filled with hydrocarbon and fluorinated chains, respectively. This leads to a fluid nanoscale multicompartment structure with kagome geometry. The thickness of the intercompartment walls is equal to the width of the π‐conjugated rods (shown as black lines).