Fukui function theorems

In a second approach of the reactivity, one fragment A is represented by its electronic density and the other, B, by some reactivity probe of A. In the usual approach, which permits to define chemical hardness, softness, Fukui functions, etc., the probe is simply a change in the total number of electrons of A. [5,6,8] More realistic probes are an electrostatic potential cf>, a pseudopotential (as in Equation 24.102), or an electric field E. For instance, let us consider a homogeneous electric field E applied to a fragment A. How does this field modify the intermolecular forces in A Again, the Hellman-Feynman theorem [22,23] tells us that for an instantaneous nuclear configuration, the force on each atom changes by... 

This issue was addressed in [2] for electron-transfer reactivities. The nuclear Fukui functions and softnesses defined there are valid for gapless systems. The analysis begins with nuclear forces specified through the Feynman-Hellmann theorem [48],... 

A local version of the electrophilicity can be obtained by multiplying to with the relevant Fukui function. These concepts play an important role in the Hard and Soft Acid and Base (HSAB) principle, which states that hard acids prefer to react with hard bases, and vice versa." By means of Koopmans theorem (Section 3.4) the hardness is... 

The experimental electrofugality in the 5 1 reactions of substituted benzhydryl phenyl sulflnates is directly related to the theoretical electrofugality calculated using Koopman s theorem and nucleophilic Fukui functions.It is suggested that the... 

This implies that the nuclear Fukui function can also be interpreted in terms of the contributions to binding (//r) < 0) and antibinding (/ (r) < 0) regions in the moleeule within the framework of Berlin s theorem. Illustrative examples and applications of this function have been performed. Also... 

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