Role of electronic kinetic energy and resultant gradient information in chemical reactivity.

The role of resultant gradient-information concept, reflecting the kinetic energy of electrons, in shaping the molecular electronic structure and reactivity preferences of open reactants is examined. This quantum-information descriptor combines contributions due to both the modulus (probability) and phase (current) components of electronic wavefunctions. The importance of resultant entropy/information concepts for distinguishing the bonded (entangled) and nonbonded (disentangled) states of molecular fragments is emphasized and variational principle for the minimum of ensemble-average electronic energy is interpreted as a physically equivalent rule for the minimum of resultant gradient-information, and the information descriptors of charge-transfer (CT) phenomena are introduced. The in situ reactivity criteria, represented by the populational CT derivatives of the ensemble-average values of electronic energy or resultant information, are mutually related, giving rise to identical predictions of electron flows in the acid(A) - base(B), reactive systems. The virial theorem decomposition of electronic energy is used to reveal changes in the resultant information content due to the chemical bond formation, and to rationalize the Hammond postulate of reactivity theory. The complementarity principle of structural chemistry is confronted with the regional hard (soft) acid and bases (HSAB) rule by examining the polarizational and relaxational flows in such acceptor-donor reactive systems, responses to the external potential and CT displacements, respectively. The frontier-electron basis of the HSAB principle is reexamined and the intra- and inter-reactant communications in A-B systems are explored.