Hydrogen bond angles distortion

In reality, several factors were mentioned as being responsible for this behavior, such as variations in bond angle distortion, in the internal stress or in the hydrogen content [40, 76], but all of them are also strongly correlated with the variation of optical gap width in amorphous carbon films. Theoretical work on Raman spectroscopy on DLC materials gave additional support for Dillon s interpretation [77]. 

Fig. 2.6 Comparison of the calculated structures for glycine in the gas-phase and in water (COSMO solvation model). Note that the central bond angle in the zwitterionic form 1 is distorted by the hydrogen bond length of 1.96A computed for this structure in the gas phase. When solvation effects are included in the calculation using COSMO, the electrostatic interaction is reduced in magnitude due to charge screening by water, and the bond angle distortion is no longer present.

Methane, CH4, for example, has a central carbon atom bonded to four hydrogen atoms and the shape is a regular tetrahedron with a H—C—H bond angle of 109°28, exactly that calculated. Electrons in a lone pair , a pair of electrons not used in bonding, occupy a larger fraction of space adjacent to their parent atom since they are under the influence of one nucleus, unlike bonding pairs of electrons which are under the influence of two nuclei. Thus, whenever a lone pair is present some distortion of the essential shape occurs. 

Table 1 Hsts some of the physical properties of duoroboric acid. It is a strong acid in water, equal to most mineral acids in strength and has a p p o of —4.9 as compared to —4.3 for nitric acid (9). The duoroborate ion contains a neady tetrahedral boron atom with almost equidistant B—F bonds in the sohd state. Although lattice effects and hydrogen bonding distort the ion, the average B—F distance is 0.138 nm the F—B—F angles are neady the theoretical 109° (10,11). Raman spectra on molten, ie, Hquid NaBF agree with the symmetrical tetrahedral stmcture (12).

The Z,Z,Z,Z,Z-isomer is required by geometry to have bond angles of 144° to maintain planarity and would therefore be enormously destabilized by distortion of the normal trigonal bond angle. The most stable structure is a twisted form of the , Z,Z,Z,Z-isomer. MO (MP2/DZd) calculations suggest an aromatic stabilization of almost ISkcal for a conformation of the , Z,Z,Z,Z-isomer in which the irmer hydrogens are twisted out of the plane by about 20°, but other calculations point to a polyene structure. ... 

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