Elucidating the Electronic Origins of Intermolecular Forces in Crystalline Solids

It is not possible to study almost any physical system without considering intermolecular forces (IMFs), no matter how insignificant they may appear relative to other energetic factors. Countless studies have shown that IMFs are responsible for governing a wide variety of physical properties, but often the atomic-origins of such interactions elude experimental detection. A considerable amount of work throughout the course of this research was therefore placed on using quantum mechanical simulations, specifically density functional theory (DFT), to calculate the electronic properties of solid-materials. The goal of these calculations was a better understanding of the precise origins of interatomic energies, down to the single-electron level. Furthermore, experimental X-ray diffraction and terahertz spectroscopy were both utilized because they are able to broadly probe the potential energy surfaces of molecular crystals, enhancing the theoretical data. Combining DFT calculations with experimental measurements enabled in-depth studies into the nature of specific non-covalent interactions, with results that were often unexpected based on conventional descriptions of IMFs. Overall, this work represents a significant advancement in understanding how subtle changes in characteristics like orbital occupation or electron density can have profound effects on bulk properties, highlighting the fragile relationship that exists between the numerous energetic parameters occurring within condensed phase systems

Concomitant polymorphism and the martensitic-like transformation of an organic crystal.

Crystalline polymorphism is a phenomenon that occurs in many molecular solids, resulting in a diverse range of possible bulk structures. Temperature and pressure can often be used to thermodynamically control which crystal form is preferred, and the associated transitions between polymorphic phases are often discontinuous and complete. N-Methyl-4-carboxypyridinium chloride is a solid that undergoes an apparent continuous temperature-dependent phase transition from an orthorhombic to a monoclinic polymorph. However, a hybrid characterization approach using single-crystal X-ray diffraction, terahertz time-domain spectroscopy, and solid-state density functional theory reveals the transformation to be actually a slowly changing ratio of the two discrete polymorphic forms. The potential energy surface of this process can be directly accessed using terahertz radiation, and the data show that a very low barrier (43.3 J mol-1) exists along the polymorph transformation coordinate

Finite Element Modeling of Wood Bat Profiles for Durability

AbstractThe bats used in Major League Baseball (MLB) are required to be turned from a single piece of wood. Northern white ash had been the wood of choice until the introduction of hard maple in the late 1990s. Since the introduction of maple to the game, there was a perceived increase in the rate of bats to exhibit multiple piece failures (MPF)—both ash and maple. These failures introduced a new aspect to the game that can be a significant factor during play, i.e. pieces of bats going into the field of play, thereby distracting fielders while reacting to the batted ball. Observations of bat breakage in the field and lab testing of bats in controlled conditions have shown the bat durability is a function of wood quality and bat profile. Wood quality is described by the density and the slope of grain of the wood used in the bat. The density and the slope of grain determine the effective strength of the wood. The bat profile is described by the variation in the diameter of the bat along its length. The wood densities and bat profiles which are preferred by players, are typically in direct contradiction with what makes for a durable bat. In this paper, the finite element method is used to develop calibrated models of the breaking of wood bats in controlled lab conditions. The modeling approach is then used to explore how bat profile influences bat durability and what potential changes can be made in bat profile to satisfy player desires while increasing bat durability

Food contact of paper and plastic products containing SiO2, Cu-Phthalocyanine, Fe2O3, CaCO3: Ranking factors that control the similarity of form and rate of release

The paper industry is an important sector annually consuming kilotons of nanoforms and non-nanoforms of fillers and pigments. Fillers accelerate the rate of drying (less energy needed) and product cost (increasing the load of low-cost fillers). The plastic industry is another use sector, where coloristic pigments can be in nanoform, and many food containers are made of plastic. Use of paper to wrap both wet and dry food is consumer practice, but not always intended by producers. Here we compare the release behavior of different nano-enabled products (NEPs) by changing a) nanoform (NF) characteristics, b) NF load, c) the nano-enabled product (NEP) matrix, and d) food simulants. The ranking of these factors enables an assessment of food contact by concepts of analogy, specifically via the similarities of the rate and form of release in food during contact. Three types of matrices were used: Paper, plastic ((Polylactic Acid (PLA), Polyamide (PA6), and Polyurethane (PU)), and a paint formulation. Two nanoforms each of SiO2, Fe2O3, Cu-Phthalocyanine were incorporated, additionally to the conventional form of CaCO3 that is always contained in paper to reduce cellulose consumption. Tests were guided by the European Regulation EC 1935/2004 and EU 10/2011. No evidence of particle release was observed: the qualitative similarity (the form of release) was high regarding the food contact of all NEPs with embedded NFs. Quantitative similarity of releases depended primarily on the NEP matrix, as this controls the penetration of the simulant fluid into the NEP. The solubility of the NF and impurities in the simulant fluid was the second decisive factor, as dissolution of the NF inside the NEP is the main mechanism of release. This led to complete removal of CaCO3 in acidic medium, whereas Fe and Si signals remained in the paper, consistent with the low release rates in an ionic form. In our set of 16 NEPs, only one NEP showed a dependence on the REACH NF descriptors (substance, size, shape, surface treatment, crystallinity, impurities), specifically attributed to differences in soluble impurities, whereas for all others the substance of the nanoform was sufficient to predict a similarity of food contact release, without influences of size, shape, surface treatment and crystallinity

Quantification of cation-anion interactions in crystalline monopotassium and monosodium glutamate salts.

Crystalline salt compounds composed of metal cations and organic anions are becoming increasingly popular in a number of fields, including the pharmaceutical and food industries, where such formulations can lead to increased product solubility. The origins of these effects are often in the interactions between the individual components in the crystals, and understanding these forces is paramount for the design and utilisation of such materials. Monosodium glutamate monohydrate and monopotassium glutamate monohydrate are two solids that form significantly different structures with correspondingly dissimilar dynamics, while their chemistry only differs in cation identity. Crystals of each were characterised experimentally with single-crystal X-ray diffraction and terahertz time-domain spectroscopy and theoretically using solid-state density functional theory simulations, in order to explain the observed differences in their bulk properties. Specifically, crystal orbital overlap and Hamiltonian population analyses were performed to examine the role that the individual interactions between the cation and anion played in the solid-state structures and the overall energetic profiles of these materials