Core electron topologies in chemical bonding

Since the discovery of silicon and Wöhler's success in cheating nature by synthesizing organic compounds, Wöhler himself was among the first (in mid-19th century) to suggest replacing carbon by silicon in organic compounds. It became clear in the early 20th century that silicon does not have a chemistry similar to carbon, and dreams of silicon-based life only survive in science fiction. We know empirically that carbon has the capability to form a variety of unsaturated compounds, which silicon has not. However, the root cause of why only carbon has such capability has remained a mystery. Quantum chemical calculations of unprecedented accuracy carried out at YNU reveal that core electrons (which were not supposed to participate in chemical bonding) have a very different role in the unsaturated compounds of carbon and silicon. Carbon has the propensity to alter the topology (nodal structure) of its core electrons, which for C₂ results to the formation of a torus like ring in the 1?g orbital formed of C1s electrons. Si₂, however, maintains the spherical like core orbitals centered at each atomic site in all its molecules. This flexibility of carbon's core orbitals allows carbon to form a cornucopia of different valence bond structures, whereas silicon is restricted to bond structures orthogonal to the atomic like spherical core orbitals.

The impact of this discovery can be far reaching. Core electrons have thus far been assumed more or less inert, but perhaps it becomes necessary to reassess their contribution to chemical bonding -- at least in the case of unsaturated bonds. Finally, it is suggested that other elements, such as nitrogen, phosphorus, and fluorine, exhibit similar flexibility to modify their core electron topologies, and thus, exhibit similarly rich chemistries.