Molecules, electron diffraction

Figure 2. Diffraction camera for single-molecule electron diffraction. A Lanthanum hexaboride electron source is used. The laser and associated optics is rotated after each data readout for a new molecular beam orientation. Organic molecules are picked up within liquid helium droplets to form a molecular beam traversing the electron beam.

Optical examination of etched polished surfaces or small particles can often identify compounds or different minerals hy shape, color, optical properties, and the response to various etching attempts. A semi-quantitative elemental analysis can he used for elements with atomic number greater than four by SEM equipped with X-ray fluorescence and various electron detectors. The electron probe microanalyzer and Auer microprobe also provide elemental analysis of small areas. The secondary ion mass spectroscope, laser microprobe mass analyzer, and Raman microprobe analyzer can identify elements, compounds, and molecules. Electron diffraction patterns can be obtained with the TEM to determine which crystalline compounds are present. Ferrography is used for the identification of wear particles in lubricating oils. 

As noted earlier, most electron diffraction studies are perfonned in a mode of operation of a transmission electron microscope. The electrons are emitted themiionically from a hot cathode and accelerated by the electric field of a conventional electron gun. Because of the very strong interactions between electrons and matter, significant diffracted intensities can also be observed from the molecules of a gas. Again, the source of electrons is a conventional electron gun. 

For bulk structural detemiination (see chapter B 1.9). the main teclmique used has been x-ray diffraction (XRD). Several other teclmiques are also available for more specialized applications, including electron diffraction (ED) for thin film structures and gas-phase molecules neutron diffraction (ND) and nuclear magnetic resonance (NMR) for magnetic studies (see chapter B1.12 and chapter B1.13) x-ray absorption fine structure (XAFS) for local structures in small or unstable samples and other spectroscopies to examine local structures in molecules. Electron microscopy also plays an important role, primarily tlirough unaging (see chapter B1.17). 

Physical, chemical, and biological properties are related to the 3D structure of a molecule. In essence, the experimental sources of 3D structure information are X-ray crystallography, electron diffraction, or NMR spectroscopy. For compounds without experimental data on their 3D structure, automatic methods for the conversion of the connectivity information into a 3D model are required (see Section 2.9 of this Textbook and Part 2, Chapter 7.1 of the Handbook) [16]. 

D Molecule Representation of Structures Based on Electron Diffraction Code (3D MoRSE Code)... 

The tnhahdes of phosphoms usually are obtained by direct halogenation under controlled conditions, eg, in carbon disulfide solution in the case of the triiodide. Phosphoms trifluoride [7647-19-0] is best made by transhalogenation of PCl using AsF or Cap2. AH of the phosphoms tnhahdes are both Lewis bases and acids. The phosphoms tnhahdes rapidly hydroly2e in water and are volatile. Examination by electron diffraction has confirmed pyramidal stmctures for the gaseous tnhahde molecules (36). Physical properties and heat of formation of some phosphoms hahdes are hsted in Table 7. 

Electron diffraction studies indicate that phosphoms pentoxide vapor consists of P O q molecules. The vapor usually condenses to the hexagonal crystalline modification but under rapid cooling can be condensed to an amorphous soHd (P-form). The Hquid obtained by melting the stable orthorhombic modification cools to form a glass which is the P-form. The Hquid obtained from the H modification also can be supercooled to a glass. 

One important structural feature on which to focus is whether the nitrogen atom lies in the same plane as the three carbon atoms. Electron diffraction experiments have found the ground state to be slightly non-planar. You can determine the planarity of the structures you compute by examining the sum of the three C-N-C angles (for a planar molecule, the sum will be 360°) and by looking at the values of the C2-N-C4-O and C3-N-C4 Hg dihedral angles (in a planar structure, both will be 0°). 

Figure 17.16 Molecular structure and dimensions of gaseous molecules of chlorine oxides as determined by microwave spectroscopy (CI2O and CIO2) or electron diffraction (CI2O7).

The addition of solid Ba2Xe06 to cold cone H2SO4 produces the second known oxide of xenon, Xe04. This is an explosively unstable gas which may be condensed in a liquid nitrogen trap. The solid tends to detonate when melted but small sublimed crystals have been shown to melt sharply at —35.9°C. Xe04 has only been incompletely studied, but electron diffraction and infrared evidence show the molecule to be tetrahedral. 

In theory, electron diffraction measurements on gaseous molecules are somewhat sensitive to the thermal motions of the atoms,... 

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