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RESEARCH PRODUCT

Nonlocal (Pair Site) Reactivity from Second-Order Static Density Response Function:  Gas- and Solution-Phase Reactivity of the Acetaldehyde Enolate as a Test Case

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A nonlocal (pair site) reactivity scheme is developed and tested. The theory is cast in terms of the first-order Fukui response function f(r,r‘), previously proposed by Fuentealba and Parr [J. Chem. Phys. 1991, 94, 5559]. A change of variables is introduced by using the softness s(r) and t(r) = [∂s(r)/∂N]υ(r) (the variation of softness with respect to the changes in the total number of electrons N at constant external potential υ(r)) that leads to a simple expression for the variation of the Fukui function at site k, namely = − for an electrophilic attack. The first term describes a local contribution, proportional to the variation of the electrostatic potential that can be induced, for example, by the approach of an electrophilic agent, with a variable global softness coefficient thereby incorporating higher (third) order derivatives of the electronic energy. The second term contains nonlocal information implicitly involving a second reactive site that is expressed in terms of the variations to the elect...