Elementary Derivation of the "|Δµ| Big Is Good" Rule.

ABSTRACT

Thirty years ago, Parr and Yang postulated that favorable chemical processes are associated with large changes in the electronic chemical potential or, equivalently, the electronegativity. They called this the "|Δµ| big is good" rule and noted that if the rule could be justified, then it "would constitute a validation of frontier theory from first principles." We provide a simple and insightful justification for the "|Δµ| big is good" rule, with special emphasis on electron-transfer reactions. Furthermore, we show that it implies Pearson's hard/soft acid/base principle mathematically and confirm this result with numerical examples. This supports Parr's intuition that many other reactivity precepts arise as corollaries to the more fundamental "|Δµ| big is good" rule. In all of this, it is essential to consider the intensive nature of the chemical potential.