Singly occupied molecular orbital dissociation energy

Figure 20-7. B3LYP/6-31++G" calculated adiabatic and vertical potential energy surfaces (PESs) of C5 -05/ bond dissociation of 5 -dTMPH radical anion. Energies and distances are given in kcal/mol and angstroms (A), respectively. The singly occupied molecular orbital (SOMO) is also shown. (Reprinted with permission from ref. [209], J. Phys. Chem. (2007) American Chemical Society.)...

In this calculation, the potential energy surface (PES) for Cs -Os bond dissociation of 5 -dTMPH in vertical and adiabatic states was calculated using both compact (6-31G ) and diffuse (6-31++G ) basis sets. At each step on the PES, the singly occupied molecular orbital (SOMO)... 

The treatment may be extended to deal with the energy of alkyl radicals if one assumes that the single unpaired elect on on the radicalized carbon atom occupies of 2p7T molecular orbital and does not change the interaction of other electrons on other orbitals. As mentioned earlier this assumption is in accord with ESR-investi-gations [4]. In electronic terms the dissociation eijergy D of a bond Ri — R2 can then be formulated as... 

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