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Molecular Crystals

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Chemical Physics of Molecular Condensed Matter

Part of the book series: Lecture Notes in Chemistry ((LNC,volume 104))

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Abstract

After seeing the entropic mechanism of crystallization, which is fundamental, we acquire an idea of its theoretical treatment within the Landau theory. Some issues closely related to the so-called crystal engineering, such as packing of anisotropic molecules and lattice energy, are introduced. A new definition of crystals covers not only the traditional crystals that are periodic in the three-dimension but also other regular solids, which exhibit sharp diffractograms similarly to the traditional crystals when irradiated by appropriate radiations.

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Notes

  1. 1.

    A numerical factor to correctly normalize is not a matter here. These can be adjusted in chosing expansion coefficients, u, v and w.

  2. 2.

    Generally, the scattering power of scatterers, such as atoms, is a function of scattering vector \(\textit{\textbf{q}}\).

  3. 3.

    Note that “i” in formulas in this section is the imaginary unit, i.e., \(i^2=-1\) while “j” is an integer index.

  4. 4.

    This argument applies to smooth modulation waves, such as a sinusoidal one. If the structural modulation on each site is discrete, the energy is equal before and after its shift, but the activation energy is necessary.

  5. 5.

    Crystalline packings with complete mechanical stability as low as its packing density of \(\pi /4\sqrt{2}\) (\({\approx }\,0.55\)) are known for hard spheres [28].

  6. 6.

    The structure of an ET molecule is shown in Fig. 8.4. Other charge-transfer salts such (ET)\(\cdot \)I\(_3\) [36] and solvated ones such as (ET)\(\cdot \)I\(_3\)(TCE)\(_{0.33}\) (TCE: trichloroethane) [37] are known, but these are not polymorphs of (ET)\(_2\)I\(_3\).

  7. 7.

    If the transition takes several tens hours [38, 39], one may miss it, leading to a practical identification of polymorphism.

  8. 8.

    The glass transition on heating.

  9. 9.

    Different definitions may be used for the Madelung constant. For example, it can be based on not the lattice constant but the distance between adjacent ions.

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Authors and Affiliations

  1. Department of Chemistry Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Japan

    Kazuya Saito

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Saito, K. (2020). Molecular Crystals. In: Chemical Physics of Molecular Condensed Matter. Lecture Notes in Chemistry, vol 104. Springer, Singapore. https://doi.org/10.1007/978-981-15-9023-8_4

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