Search

Different procedures to obtain atom condensed Fukui functions are described. It is shown how the resulting values may differ depending on the exact approach to atom condensed Fukui functions. The condensed Fukui function can be computed using either the fragment of molecular response approach or the response of molecular fragment approach. The two approaches are nonequivalent; only the latter approach corresponds in general with a population difference expression. The Mulliken approach does not depend on the approach taken but has some computational drawbacks. The different resulting expressions are tested for a wide set of molecules. In practice one must make seemingly arbitrary choices about how to compute condensed Fukui functions, which suggests questioning the role of these indicators in conceptual density-functional theory. [ABSTRACT FROM AUTHOR]

Abstract: In analogy to the electrophilicity and the potentialphilicity, we define the chargephilicity and chargephobicity to describe the energetic response of a molecule to a change in its charge distribution. The chargephilicity captures the ‘best’ way to change the underlying charge distribution; the chargephobicity captures the ‘worst’ way to change the underlying charge distribution. The Coulomb potential induced by the linear-response function plays a very important role in this approach, analogous to the role of the hardness for the electrophilicity, the hardness kernel for the Fukui function, and the linear-response function for the potentialphilicity and potentialphobicity. [Copyright &y& Elsevier]