Dissociation of chemical bonds

Equation (12.8) offers promising new fields of applications regarding the dissociation of chemical bonds. 

In thermal oxidation, initiation (1) results Irom the thermal dissociation of chemical bonds that may arise Irom intrinsically weak links formed as by-products of the polymerization reaction (e.g. head-to-head links) or impurities formed in the polymerization reactor such as hydroperoxides, POOH, or in-chain peroxides as occur in polystyrene from oxygen scavenging. Reaction (1 ) shows that POOH may produce peroxy and alkoxy radicals that may subsequently form alkyl radicals via reaction (3). 

In the Hartree-Fock method, electrons of opposite spins do not correlate their motion which is an absurd situation (in contrast to when electmis of the same spins avoid each other, which is reasonable). In many cases (like the F2 molecule, description of dissociation of chemical bonds, or interaction of atoms and npolar molecules), this leads to wrong results. In this chapter, we have learned about the methods that do take into account a correlation of electronic motions. 

The redox reactions of [MCbpyls] are classified into an outer-sphere electron-transfer reaction, in which the coordination environment of the centered metal is unchanged before and after the electron transfer. The rate for such an outer-sphere electron-transfer reaction is often fast as compared with the inner-sphere electron-transfer reactions accompanied with formation and dissociation of chemical bonds. The rate constant, k, for the outer-sphere electron-transfer reaction is given by Marcus theory [2, 21]. 

V. N. Kondratiev, Energies of Dissociation of Chemical Bonds, Akad. Nauk... 

Bernecker and Long have surveyed the enthalpies of formation of gaseous ions and Kondratiev treats the energies of dissociation of chemical bonds. 

Kondratiev, Energies of Dissociation of Chemic Bonds , Publishing House of the Academy of Sciences, U.S.S.R., Moscow, 1962. 

The formation and dissociation of chemical bonds is of prime concern in chemistry, and with the advent of ultrafast high-intensity lasers, selective bond dissociation using appropriate laser pulses as molecular tweezers and scissors has received extensive and intense attention. - Theoretical approaches to laser-assisted control of chemical reactions have kept pace and demonstrated remarkable success, with experimental results reinforcing the theoretical ideas. The development of... 

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