Mesomorphology of clathrate hydrates from molecular ordering.

Clathrate hydrates are crystals formed by guest molecules that stabilize cages of hydrogen-bonded water molecules. Whereas thermodynamic equilibrium is well described via the van der Waals and Platteeuw approach, the increasing concerns with global warming and energy transition require extending the knowledge to non-equilibrium conditions in multiphase, sheared systems, in a multiscale framework. Potential macro-applications concern the storage of carbon dioxide in the form of clathrates, and the reduction of hydrate inhibition additives currently required in hydrocarbon production. We evidence porous mesomorphologies as key to bridging the molecular scales to macro-applications of low solubility guests. We discuss the coupling of molecular ordering with the mesoscales, including (i) the emergence of porous patterns as a combined factor from the walk over the free energy landscape and 3D competitive nucleation and growth and (ii) the role of molecular attachment rates in crystallization-diffusion models that allow predicting the timescale of pore sealing. This is a perspective study that discusses the use of discrete models (molecular dynamics) to build continuum models (phase field models, crystallization laws, and transport phenomena) to predict multiscale manifestations at a feasible computational cost. Several advances in correlated fields (ice, polymers, alloys, and nanoparticles) are discussed in the scenario of clathrate hydrates, as well as the challenges and necessary developments to push the field forward.

Nanocrystal Assemblies: Current Advances and Open Problems.

We explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.