Block copolymers (BCPs) are important for technological advances in numerous industries, including but not limited to, electronics, biomedical, optics, environmental, and infrastructure. Because of their ubiquity, it is important to understand their hierarchical phase behavior to tune their macroscopic properties for efficient use. These macroscopic properties are derived from the microscopic self‐assembled structures. One unique form of hierarchical assembly exists when one or more of the polymeric blocks form lamellar crystals. These crystals are integral to understanding and predicting the macroscopic behavior. This review reports on recent advances in crystallization of BCPs, including bulk and solution assembly. Reports highlighting development in fundamental processes regarding crystallization mechanisms and behavior as well as for the design of practical applications are included.

A crystal structure prediction (CSP) workflow, based on the random structure generator, Genarris, and the genetic algorithm (GA), GAtor, is applied to the energetic materials 2,4,6-trinitrobenzene-1,3,5-triamine (TATB) and 2,4,6-trinitrobenzene-1,3-diamine (DATB),...

Molecular crystals of energetic materials (EMs) are denser than typical molecular crystals and are characterized by distinct intermolecular interactions between nitrogen-containing moieties. To assess the performance of dispersion-inclusive density functional theory (DFT) methods, we have compiled a data set of experimental sublimation enthalpies of 31 energetic materials. We evaluate the performance of three methods: the semilocal Perdew–Burke–Ernzerhof (PBE) functional coupled with the pairwise Tkatchenko-Scheffler (TS) dispersion correction, PBE with the many-body dispersion (MBD) method, and the PBE-based hybrid functional (PBE0) with MBD. Zero-point energy contributions and thermal effects are described using the quasi-harmonic approximation (QHA), including explicit treatment of thermal expansion, which we find to be non-negligible for EMs. The lattice energies obtained with PBE0+MBD are the closest to experimental sublimation enthalpies with a mean absolute error of 9.89 kJ/mol. However, the state-of-the-art treatment of vibrational and thermal contributions makes the agreement with experiment worse. Pressure–volume curves are also examined for six representative materials. For pressure–volume curves, all three methods provide reasonable agreement with experimental data with mean absolute relative errors of 3% or less. Most of the intermolecular interactions typical of EMs, namely nitro-amine, nitro–nitro, and nitro-hydrogen interactions, are more sensitive to the choice of the dispersion method than to the choice of the exchange-correlation functional. The exception is π–π stacking interactions, which are also very sensitive to the choice of the functional. Overall, we find that PBE+TS, PBE+MBD, and PBE0+MBD do not perform as well for energetic materials as previously reported for other classes of molecular crystals. This highlights the importance of testing dispersion-inclusive DFT methods for diverse classes of materials and the need for further method development.