By D. Braga, F. Greponi
An outstanding review of the manifold elements of recent crystal engineering. From layout and education to spectroscopy and functions, this guide either covers and evaluates all elements of crystal engineering. essentially dependent, it presents an outline of the present prestige as noticeable from its a variety of angles in addition to a comparability of alternative suggestions and applications.An crucial resource of top quality details for everybody operating during this booming and interdisciplinary box: spectroscopists, actual and inorganic chemists in addition to fabrics scientists operating in nanotechnology and the pharmaceutical undefined.
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Additional resources for Making Crystals by Design. Methods, Techniques and Applns
In organic crystals lattice vibrational frequencies fall in a rather restricted range, something like 30–150 cm–1, and even k-spreading cannot bring about major differences. 1 Supramolecular Interactions: Energetic Considerations corresponding vibrational entropies cannot be too different. Enthalpy differences between polymorphs must be small because the potentials are anyway weak and almost isotropic, and entropy differences follow suit, because the force constants (the second derivatives of these potentials) also cannot be too different.
One sees there a clear predominance of dispersion in hydrocarbon crystals, an increased relevance of coulombic and polarization effects in heteroatom-containing molecules, and the clear predominance of coulombic-polarization energies in hydrogen-bonded crystals. In fact, a plot of the partitioned energies in hydrogen-bonded dimers shows that the total energy up to an O···H distance equal to the equilibrium value coincides almost exactly with the coulombic contribution. While of course the partitioning is to a large extent arbitrary and depends on the values of the parameters in the theory, the picture of intermolecular bonding is, within the present parametrization, quite convincing and helps explaining some of the main packing factors in crystals.
Following the usual procedure, in the water dimer one can draw lines that connect the bonded atoms. The usual graphical representation of the dominant interactions for this dimer are thus obtained (see Fig. 3(a)), showing four intramolecular O–H bonds and one intermolecular H···O bond, the latter more commonly described as an O–H···O intermolecular bond. Given the energetic stability of the water dimer and the existence of only one critical point (the H···O bond critical point), the bond nature of the O–H···O intermolecular bond is well-established using rigorous quantum mechanical concepts.