Atomic Clusters: Structure, Reactivity, Bonding, and Dynamics

Atomic clusters lie somewhere in between isolated atoms and extended solids with distinctly different reactivity patterns. They are known to be useful as catalysts facilitating several reactions of industrial importance. Various machine learning based techniques have been adopted in generating their global minimum energy structures. Bond-stretch isomerism, aromatic stabilization, Rener-Teller effect, improved superhalogen/superalkali properties, and electride characteristics are some of the hallmarks of these clusters. Different all-metal and nonmetal clusters exhibit a variety of aromatic characteristics. Some of these clusters are dynamically stable as exemplified through their fluxional behavior. Several of these cluster cavitands are found to be agents for effective confinement. The confined media cause drastic changes in bonding, reactivity, and other properties, for example, bonding between two noble gas atoms, and remarkable acceleration in the rate of a chemical reaction under confinement. They have potential to be good hydrogen storage materials and also to activate small molecules for various purposes. Many atomic clusters show exceptional opto-electronic, magnetic, and nonlinear optical properties. In this Review article, we intend to highlight all these aspects.

Phase Behaviour of Methane Hydrates in Confined Media

In a study designed to investigate the melting behaviour of natural gas hydrates which are usually formed in porous mineral sediments rather than in bulk, hydrate phase equilibria for binary methane and water mixtures were studied using high-pressure differential scanning calorimetry in mesoporous and macroporous silica particles having controlled pore sizes ranging from 8.5 nm to 195.7 nm. A dynamic oscillating temperature method was used to form methane hydrates reproducibly and then determine their decomposition behaviour—melting points and enthalpies of melting. Significant decreases in dissociation temperature were observed as the pore size decreased (over 6 K for 8.5 nm pores). This behaviour is consistent with the Gibbs–Thomson equation, which was used to determine hydrate–water interfacial energies. The melting data up to 50 MPa indicated a strong, essentially logarithmic, dependence on pressure, which here has been ascribed to the pressure dependence of the interfacial energy in the confined media. An empirical modification of the Gibbs–Thomson equation is proposed to include this effect.

Dimensional confinement and waveguide effect of Dyakonov surface waves in twisted confined media

We theoretically study Dyakonov surface waveguide modes that propagate along the planar strip interfacial waveguide between two uniaxial dielectrics. We demonstrate that owing to the one-dimensional electromagnetic confinement, Dyakonov surface waveguide modes can propagate in the directions that are forbidden for the classical Dyakonov surface waves at the infinite interface. We show that this situation is similar to a waveguide effect and formulate the resonance conditions at which Dyakonov surface waveguide modes exist. We demonstrate that the propagation of such modes without losses is possible. We also consider a case of two-dimensional confinement, where the interface between two anisotropic dielectrics is bounded in both orthogonal directions. We show that such a structure supports Dyakonov surface cavity modes. Analytical results are confirmed by comparing with full-wave solutions of Maxwell’s equations. We believe that our work paves the way toward new insights in the field of surface waves in anisotropic media.

Spontaneous shrinking of soft nanoparticles boosts their diffusion in confined media

Improving nanoparticles (NPs) transport across biological barriers is a significant challenge that could be addressed through understanding NPs diffusion in dense and confined media. Here, we report the ability of soft NPs to shrink in confined environments, therefore boosting their diffusion compared to hard, non-deformable particles. We demonstrate this behavior by embedding microgel NPs in agarose gels. The origin of the shrinking appears to be related to the overlap of the electrostatic double layers (EDL) surrounding the NPs and the agarose fibres. Indeed, it is shown that screening the EDL interactions, by increasing the ionic strength of the medium, prevents the soft particle shrinkage. The shrunken NPs diffuse up to 2 orders of magnitude faster in agarose gel than their hard NP counterparts. These findings provide valuable insights on the role of long range interactions on soft NPs dynamics in crowded environments, and help rationalize the design of more efficient NP-based transport systems.

Confinement Effect of Micro- and Mesoporous Materials on the Spectroscopy and Dynamics of a Stilbene Derivative Dye

Micro- and mesoporous silica-based materials are a class of porous supports that can encapsulate different guest molecules. The formation of these hybrid complexes can be associated with significant alteration of the physico-chemical properties of the guests. Here, we report on a photodynamical study of a push–pull molecule, trans-4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), entrapped within faujasite-type zeolites (HY, NaX, and NaY) and MCM-41 in dichloromethane suspensions. The complex formation gives rise to caged monomers and H- and J-aggregates. Steady-state experiments show that the nanoconfinement provokes net blue shifts of both the absorption and emission spectra, which arise from preferential formation of H-aggregates concomitant with a distortion and/or protonation of the DCM structure. The photodynamics of the hybrid complexes are investigated by nano- to picosecond time-resolved emission experiments. The obtained fluorescence lifetimes are 65–99 ps and 350–400 ps for H- and J-aggregates, respectively, while those of monomers are 2.46–3.87 ns. Evidences for the presence of a charge-transfer (CT) process in trapped DCM molecules (monomers and/or aggregates) are observed. The obtained results are of interest in the interpretation of electron-transfer processes, twisting motions of analogues push–pull systems in confined media and understanding photocatalytic mechanisms using this type of host materials.

Stochastic electromagnetic field propagation— measurement and modelling

This paper reviews recent progress in the measurement and modelling of stochastic electromagnetic fields, focusing on propagation approaches based on Wigner functions and the method of moments technique. The respective propagation methods are exemplified by application to measurements of electromagnetic emissions from a stirred, cavity-backed aperture. We discuss early elements of statistical electromagnetics in Heaviside's papers, driven mainly by an analogy of electromagnetic wave propagation with heat transfer. These ideas include concepts of momentum and directionality in the realm of propagation through confined media with irregular boundaries. We then review and extend concepts using Wigner functions to propagate the statistical properties of electromagnetic fields. We discuss in particular how to include polarization in this formalism leading to a Wigner tensor formulation and a relation to an averaged Poynting vector. This article is part of the theme issue ‘Celebrating 125 years of Oliver Heaviside's ‘Electromagnetic Theory’’.