Chemical Hardness by Sen K.D.

By Sen K.D.

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43 Structure and Bonding, Vol. ~Springer-Verlag Berlin Heidelberg 1993 28 Jos6 L. Gfizquez 1 Introduction The principle of hard and soft acids and bases [I] (HSAB), and the principle of electronegativity equalization 1,2], together with frontier orbital theory 1,3] have been, over the years, very useful to establish the behavior of molecules under different circumstances, their reactive sites, and possible reaction mechanisms [4]. Through these principles, and through the values of the parameters associated with them: hardness, softness, and electronegativity, it has been possible to correlate and to analyze experimental information that allows one to characterize the interactions involved between different chemical species in many different situations.

52) can be written in the form [12, 35] AE, ~ 1 (rt~ - ~t~)2 2 rl~, + rl~ (53) which is given in terms of the initial values of the reactivity indexes. Since AEv < 0, for a given chemical potential difference, the stabilization is larger when A and B are soft. In the case of Eq. (51) one can make use of the approximate additivity of the softness of the constitutive parts [18, 36] to evaluate the softness of the system AB. In general, SAB = k'(s~ + s~) (54) where k' is a proportionality constant.

33 5 The Interaction Energy and the Principle of Maximum Hardness . . . . . . . . . Acids and Bases . . . . . . . . . . . . . . . 38 7 Scaling Properties of Simple Functionals . . . . . . . . . . . . . . . . . . 40 8 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . 42 9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43 Structure and Bonding, Vol.

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