Chemical bonds from through-bridge orbital communications in prototype molecular systems

The indirect components of chemical interactions between atomic orbitals are explored within the Orbital Communication Theory of the chemical bond. The conditional probabilities for such through-bridge probability propagation and the associated entropy/information measures of the bond covalency are examined. The illustrative example of the bridge components of the chemical bonds between bridgehead carbons in small propellanes is discussed using the hybrid-orbital model. The bridge pi-bonds in benzene and butadiene from the inter-orbital communications involving the single intermediate atomic orbitals are probed within the Huckel description and selected higher-orders of orbital bridges, involving several orbital intermediaries, are investigated.