Energetically deficient

One might use spectral recording in experiments in which one adds a triplet energy acceptor to the reacting system. Results from a study of the fluoran-thene(-)/10-methylphenothiazine(+) reaction are shown in Figure 28.15 [86,99]. This process is an energetically deficient system that is thought to yield its blue fluoranthene-like emission via redox-produced fluoranthene (FA) triplets ... 

The inability of 2 to initiate vinyl polymerization is not due to an energetic deficiency since the intermediate products (radicals or radical ions) formed in reactions (1) and (4) do initiate polymerization. Thus, if a mixture of N,N -dimethylaniline, a biimidazole, and a monomer such as pentaerythritol triacrylate is photolyzed, a hard polymer is formed. If the N,N-dimethylaniline is omitted, no polymerization occurs, no monomer double bond loss is evident from the infrared spectrum, and radical dimerization is observed at a rate normal for inert solvents. 

Figure 7. Comparison of the energetics of the ring expansions of phenylcarbene ( A -la) and phenylnitrene (1A2-lb), calculated at the CASPT2(8,8)/6-31 G //CASSCF(8,8)/6-31 G level.57-61 The numbers in parentheses represent corrections for the known deficiencies of CASPT2/6-31G in computing the energies of singlet phenylnitrene61 and singlet phenylcarbene.55 The small differences in the energies in Fig. 5 are a consequence of the difference between the basis sets used in the two sets of calculations.

Further layers can physisorb, one above another. The extent of charge deficiency will decrease until, after about five or six layers have physisorbed, they are energetically indistinguishable. By the time we have about a dozen layers adsorbed on the glass, we are no longer able to speak about layers, and start to talk about bulk condensate of water. At this point, more water condenses onto this mass of water, causing its weight to increase, and eventually it runs down the mirror as warm condensation. 

Chromium hexavalent, the more toxic than the tri-valent form, comes in surface waters from anneries, chemical, energetic and ceramic industries. The. stable chromate form predominates in alkali, whereas dichromate in acidic waste waters, mostly in deficiency of reductives.6... 

This discussion has focused on stoichiometric spinel structure, but nonstoichiometric spinels can exist as well. In the case of spinels that are oxygen deficient there could be significant concentrations of Mn + remaining at full charge. The results of this study suggest that such spinels may be susceptible to cation rearrangement if tliey are energetically metastable. 

Inductive effects can have very pronounced effects on the reactivity of amides and similar substrates towards nitrolysis. Chemists at the Naval Air Warfare Center (NAWC) have reported an extreme case encountered during the synthesis of the energetic 1,5-diazocine known as HNFX (86). A key step in this synthesis involves a very difficult nitrolysis of the electron deficient N-nosyl (4-nitrobenzenesulfonyl) bonds of (85). Nitrolysis with strong mixed acid requires a temperature of 70 °C for 6 weeks to achieve a yield of 16 %. The same reaction with nitric acid-triflic acid requires a temperature of 55 °C for 40 hours to achieve a 65 % yield of HNFX. The same chemists reported a similar case of N-nosyl bond nitrolysis which needed a nitrating agent composed of nitric acid-triflic acid-antimony pentafluoride. ... 

It is our current opinion that all etching anisotropy or directionality is caused by energetic particle bombardment (primarily ions but in some cases, electrons). Other factors such as the degree of fluorine deficiency in the discharge can influence the... 

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