Information origins of the chemical bond: Bond descriptors from molecular communication channels in orbital resolution

Abstract

AbstractThe flow of information in the molecular communication networks in the (condensed) atomic orbital (AO) resolution is investigated and the plane‐wave (momentum‐space) interpretation of the average Fisher information in the molecular information system is given. It is argued using the quantum‐mechanical superposition principle that, in the LCAO MO theory the squares of corresponding elements of the Charge and Bond‐Order (CBO) matrix determine the conditional probabilities between AO, which generate the molecular communication system of the Orbital Communication Theory (OCT) of the chemical bond. The conditional‐entropy (“noise,” information‐theoretic “covalency”) and the mutual‐information (information flow, information‐theoretic “ionicity”) descriptors of these molecular channels are related to Wiberg's covalency indices of chemical bonds. The illustrative application of OCT to the three‐orbital model of the chemical bond X—Y, which is capable of describing the forward‐ and back‐donations as well as the atom promotion accompanying the bond formation, is reported. It is demonstrated that the entropy/information characteristics of these separate bond‐effects can be extracted by an appropriate reduction of the output of the molecular information channel, carried out by combining several exits into a single (condensed) one. The molecular channels in both the AO and hybrid orbital representations are examined for both the molecular and representative promolecular input probabilities. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009