Chemical environments

Mosshauer effect The resonance fluorescence by y-radiation of an atomic nucleus, returning from an excited state to the ground state. The resonance energy is characteristic of the chemical environment of the nucleus and Mossbauer spectroscopy may be used to yield information about this chemical environment. Used particularly in the study of Fe. Sn and Sb compounds. 

Inelastic scattering processes are not used for structural studies in TEM and STEM. Instead, the signal from inelastic scattering is used to probe the electron-chemical environment by interpreting the specific excitation of core electrons or valence electrons. Therefore, inelastic excitation spectra are exploited for analytical EM. 

An enhancement of the simple substructure approach is the Fragment Reduced to an Environment that is Limited (FREL) method introduced by Dubois et al. [7] With the FREL method several centers of the molecule are described, including their chemical environment. By taking the elements H, C, N, O, and halogens into account and combining all bond types (single, double, triple, aromatic), the authors found descriptors for 43 different FREL centers that can be used to characterize a molecule. 

NMR spectra are basically characterized by the chemical shift and coupling constants of signals. The chemical shift for a particular atom is influenced by the 3D arrangement and bond types of the chemical environment of the atom and by its hybridization. The multiplicity of a signal depends on the coupling partners and on the bond types between atom and couphng partner. 

However, one of the most successfiil approaches to systematically encoding substructures for NMR spectrum prediction was introduced quite some time ago by Bremser [9]. He used the so-called HOSE (Hierarchical Organization of Spherical Environments) code to describe structures. As mentioned above, the chemical shift value of a carbon atom is basically influenced by the chemical environment of the atom. The HOSE code describes the environment of an atom in several virtual spheres - see Figure 10.2-1. It uses spherical layers (or levels) around the atom to define the chemical environment. The first layer is defined by all the atoms that are one bond away from the central atom, the second layer includes the atoms within the two-bond distance, and so on. This idea can be described as an atom center fragment (ACF) concept, which has been addressed by several other authors in different approaches [19-21]. 

The chemical environment foran atom m a molecule is probably niiit iie to th at molecule. Chem istry tries to find unify in g concepts an d the atom type Is on e of those unifying con cepts. For example, the AMBER force field defines five atom types for oxygens ... 

Atom types represen t the chemical environment of an atom. The atom types associated with a given force field could be hard-wired to have specific vahiesand meaning. llyperChem also allows flexible definitions of the atom types and the associated chemical en vironmen Is. Th e ch em ical en viron men t of an atom (a set of rules for defining a type) and the default rules are in a standard ASCII text file, chem.nil. included with llyperChem. You can modify this file and compile it m a binary form that llyperChem... 

We pointed out in Section 13 3 that both H and are nuclei that can provide useful structural information when studied by NMR Although a H NMR spectrum helps us infer much about the carbon skeleton of a molecule a NMR spectrum has the obvious advantage of probing the carbon skeleton directly NMR spectroscopy is analogous to H NMR in that the number of signals informs us about the number of different kinds of carbons and their chemical shifts are related to particular chemical environments... 

Parameters for elements (basis functions in ab initio methods usually derived from experimental data and empirical parameters in semi-empirical methods usually obtained from empirical data or ab initio calculations) are independent of the chemical environment. In contrast, parameters used in molecular mechanics methods often depend on the chemical environment. 

The atom type defines the chemical environment of an atom. The basic idea is that not all carbon atoms in molecules are the same and can be distinguished by the following ... 

To redefine an atom type associated with a force field, adjust the rules in the chem.rul file to represent the new chemical environment for a particular type and then compile the new types. It is always desirable to save the original chem. rul under another name prior to modifying chem.rul. Having modified chem.rul, you can... 

One of the major difficulties with molecular mechanics procedures (MMh- or otherwise) is that they almost always fail. That is, you find that force constants are not available for the molecule of interest. This is both the strength and weakness of molecular mechanics it uses atom types to introduce specific chemical environments for the atoms within a molecule (to obtain accuracy in the calculations) but then requires knowledge of force constants specific to that chemical environment (as specific as stating that an atom is in a five-member ring containing one oxygen and one carbon, for example). As the number, N, of atom types rises the number of force constants needed to describe all possible occurrences of these atom type becomes very large. For torsions, for... 

As discussed earlier in Section lOC.l, ultraviolet, visible and infrared absorption bands result from the absorption of electromagnetic radiation by specific valence electrons or bonds. The energy at which the absorption occurs, as well as the intensity of the absorption, is determined by the chemical environment of the absorbing moiety. Eor example, benzene has several ultraviolet absorption bands due to 7t —> 71 transitions. The position and intensity of two of these bands, 203.5 nm (8 = 7400) and 254 nm (8 = 204), are very sensitive to substitution. Eor benzoic acid, in which a carboxylic acid group replaces one of the aromatic hydrogens, the... 

The electrons in a molecule also have magnetic moments and set up secondary magnetic fields which partly screen each atom from the applied field. Thus atoms in different chemical environments display resonance at slightly different magnetic fields. 

One other very important attribute of photoemitted electrons is the dependence of their kinetic energy on chemical environment of the atom from which they originate. This feature of the photoemission process is called the chemical shift of and is the basis for chemical information about the sample. In fact, this feature of the xps experiment, first observed by Siegbahn in 1958 for a copper oxide ovedayer on a copper surface, led to his original nomenclature for this technique of electron spectroscopy for chemical analysis or esca. 

Analysis of Surface Molecular Composition. Information about the molecular composition of the surface or interface may also be of interest. A variety of methods for elucidating the nature of the molecules that exist on a surface or within an interface exist. Techniques based on vibrational spectroscopy of molecules are the most common and include the electron-based method of high resolution electron energy loss spectroscopy (hreels), and the optical methods of ftir and Raman spectroscopy. These tools are tremendously powerful methods of analysis because not only does a molecule possess vibrational modes which are signatures of that molecule, but the energies of molecular vibrations are extremely sensitive to the chemical environment in which a molecule is found. Thus, these methods direcdy provide information about the chemistry of the surface or interface through the vibrations of molecules contained on the surface or within the interface. 

Jets for continuous filament textile yam are typically 1 cm diameter gold—platinum ahoy stmctures with 20—500 holes of 50—200 p.m diameter. Tire yam jets are also 1 cm in diameter but typicahy use 1000—2000 holes to give the required balance of filament and yam denier. Staple fiber jets can have as many as 70,000 holes and can be made from a single dome of ahoy or from clusters of the smaller textile or tire yam jets. The precious metal ahoy is one of the few materials that can resist the harsh chemical environment of a rayon machine and yet be ductile enough to be perforated with precision. Glass jets have been used for filament production, and tantalum metal is a low cost but less durable alternative to gold—platinum. 

Each hydrogen atom in a unique chemical environment is shielded differently from the external field and has a slightly different resonance frequency. The chemical shift in ppm, 5, is defined as... 

Corrosion Resistance of the Austenitic Chromium—Mickel Stainless Steels in Chemical Environments, Inco Limited, Nickel Development Institute, Toronto, Ontario, Canada, 1963. 

The tensile and flexural properties as well as resistance to cracking in chemical environments can be substantially enhanced by the addition of fibrous reinforcements such as chopped glass fiber. Mechanical properties at room temperature for glass fiber-reinforced polysulfone and polyethersulfone are shown in Table 5. 

Resistance to Chemical Environments and Solubility. As a rule, amorphous plastics are susceptible, to various degrees, to cracking by certain chemical environments when the plastic material is placed under stress. The phenomenon is referred to as environmental stress cracking (ESC) and the resistance of the polymer to failure by this mode is known as environmental stress cracking resistance (ESCR). The tendency of a polymer to undergo ESC depends on several factors, the most important of which are appHed stress, temperature, and the concentration of the aggressive species. 

Table 8. Resistance, of Natural (Unreinforced) PSF, PES, and PPSF Resins to Various Chemical Environments ...

In spite of these special cases, in all appHed uses the decay constants and half-Hves can be considered to be independent of the physical and chemical environment. 

Value has been reported to vary up to 0.3% owing to chemical environment. 

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