Hybrid Chemical Groups

The novelty of this type of organic functionalization is explained in terms of the wide number of different methanofullerene materials that can be reached due to the presence of esters moieties either properly functionalized carbon nucleophiles can be constructed that ultimately would add to C60, or additional chemical transformation to the addend group of an already synthesized methanofullerene could occur. Thus, theoretically, any chemical group carrying novel physical, electronic, magnetic, or mechanical properties that fulfills the appropriate requirements for the construction of novel organofullerene hybrid materials can be properly designed and, thus, attached on the fullerene skeleton. 

Earlier than with pulsed chemical lasers, the first technological breakthrough in chemical lasers occurred for continuous-wave lasers. Almost simultaneously in 1968 two groups successfully operated continuous-wave chemical lasers. One was at the Aerospace Corporation headed by T. A. Jacobs 75>, the other one at Cornell University under T. A. Cool 76>. One of these lasers was an HF laser the other was that is now called a hybrid chemical laser, being pumped by energy transfer rather than by a direct chemical reaction. This laser principle has been described in the context of pulsed chemical lasers in Section 6.5, In addition to these devices, an HF cw laser having millisecond flow duration was also demonstrated in principle in a shock tunnel. The latter employed diffusion of HC1 into a supersonic stream containing F atoms 77>. 

The most conventional kinetic scheme of FRP includes initiation, propagation, and bimolecular termination reaction steps. Additional reactions such as chain transfer are introduced to improve the process description. Free radicals are highly reactive chemical species produced by the homolytic dissociation of covalent bonds. Such species are produced through physical (thermoexcitation, radiation) or chemical methods (oxidation-reduction, addition, etc.). Generally, their survival time is less than a second, except for those radicals highly stabilized by specific chemical groups the hybridization state is sp. ... 

MOFs have emerged as a novel class of porous solid-state materials with hybrid chemical composition of organic molecules bearing a wide array of functional groups capable of metal coordination and/or chelation and metal ions/clusters. Several attributes of such materials have captured the interest of scientists in academia and industry because of the wide potential applications in current demanding technologies. MOF attributes are directly correlated to the tunable hybrid chemical composition, crystallinity, and modular nature. 

It is recommended that the reader become familiar with the point-group symmetry tools developed in Appendix E before proceeding with this section. In particular, it is important to know how to label atomic orbitals as well as the various hybrids that can be formed from them according to the irreducible representations of the molecule s point group and how to construct symmetry adapted combinations of atomic, hybrid, and molecular orbitals using projection operator methods. If additional material on group theory is needed. Cotton s book on this subject is very good and provides many excellent chemical applications. 

There is one semiempirical program, called HyperNMR, that computes NMR chemical shifts. This program goes one step further than other semiempiricals by defining different parameters for the various hybridizations, such as sp carbon vs. sp carbon. This method is called the typed neglect of differential overlap method (TNDO/1 and TNDO/2). As with any semiempirical method, the results are better for species with functional groups similar to those in the set of molecules used to parameterize the method. 

---