Molecule/molecular unit structure

Figure 17.17 The structure of I2O5 showing the dimensions and conformation of a single molecular unit. Note that the molecule has no mirror plane of symmetiy so is not C2V...

Due to the steric requirement of these substituents the formation of a columnar structure with infinite M M interactions is inhibited, and only the association of pairs of molecular units is allowed. The Ni Ni distance is 3.21 A [164]. If the same compound is crystallized in the presence of benzimidazole, the [Ni(dmg-BF2)2]2 dimer units are sandwiched between sheets of benzimidazole molecules due to n-n interactions resulting in an increased Ni Ni separation of 3.358 A [165]. With anthracene the n-n interactions seem to be stronger, because in this case the parent dimer molecule is cleaved. Each monomer now has a conformation of type B (Fig. 32) and is sandwiched by anthracene molecules [166]. Compound 121 has the same configuration [163d]. 

A simple example of how molecular electronic structure can influence condensed phase liquid crystalline properties exists for molecules containing strongly dipolar units. These tend to exhibit dipolar associations in condensed phases which influence many thermodynamic properties [29]. Local structural correlations are usually measured using the Kirkwood factor g defined as... 

Since plane waves are delocalised and of infinite spatial extent, it is natural to perform these calculations in a periodic environment and periodic boundary conditions can be used to enforce this periodicity. Periodic boundary conditions for an isolated molecule are shown schematically in Fig. 8. The molecular problem then becomes formally equivalent to an electronic structure calculation for a periodic solid consisting of one molecule per unit cell. In the limit of large separation between molecules, the molecular electronic structure of the isolated gas phase molecule is obtained accurately. 

Fig. 8. Illustration of the use of periodic boundary conditions in the determination of molecular electronic structure. The unit cell is shown by the dashed line. As the unit cell size is increased the calculated properties converge toward those of the isolated molecule...

T ike metals minerals also exhibit typical crystalline structures. As an example, the structure of molybdenite is shown in Figure 1.17. It is hexagonal with six-pole symmetry and contains two molecules per unit cell. Each sulfur atom is equidistant from three molybdenum atoms and each molybdenum atom is surrounded by six sulfur atoms located at the comers of a trigonal prism. There are two types of bonds that can be established between the atoms which constitute the molybdenite crystal stmcture. They are the covalent bonds between sulfur and molybdenum atoms and the Van der Waals bonds between sulfur-sulfur atoms. The Van der Waals bond is considerably weaker than the covalent sulfur-molybdenum bond. This causes the bonds of sulfur-sulfur to cleave easily, imparting to molybdenite the property of being a dry lubricant. Molybdenite adheres to metallic surfaces with the development of a molecular bond and the friction between metallic surfaces is replaced by easy friction between two layers of sulfur atoms. 

Amylose has a lower molecular weight than amylopectin but forms linear chains while amylopectin has a higher molecular weight but forms more compact molecules. While both molecules have a structure mainly based on a-(l - 4)-D-glucose units, the amylopectin structure is branched at the a-(l - 6)-D-glucose units. 

Thermodynamically stable sulfur forms deep yellow, nonodorous orthorhombic crystals with a space group Fddd-D, containing 16 molecules, i.e., 128 atoms in the unit cell. It has a density of 2.069 gm/cm and is well soluble in CS2. Its molecular unit is Sg, cyclooctasulfur, a crown-shaped molecule with a symmetry of i>4d. The pale flowers of sulfur, prepared by alchemist by distillation, are insoluble in CS2, and the structure is not yet fully understood. Another form, plastic sulfur, is obtained by melting sulfur to about 180°C, where it forms as highly... 

If a regular single-strand chain is linked to a constitutional unit of the main chain (backbone) of a polymer molecule or to a low-molecular-weight structure, either directly or through an intervening unit, it is considered a substituent of the constitutional unit or structure. In naming the polymeric substituent, the actual bonding relations are reflected in the name of the CRU. 

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