The location of the chemical bond. Application of long covalent bond theory to the structure of silica

Oxygen is the most abundant terrestrial element and is found in a variety of materials, but still wanting is a universal theory for the stability and structural organization it confers. Herein, a computational molecular orbital analysis elucidates the structure, stability, and cooperative bonding of α-quartz silica (SiO ). Despite geminal oxygen-oxygen distances of 2.61-2.64 Å, silica model complexes exhibit anomalously large O-O bond orders (Mulliken, Wiberg, Mayer) that increase with increasing cluster size-as the silicon-oxygen bond orders decrease. The average O-O bond order in bulk silica computes to 0.47 while that for Si-O computes to 0.64. Thereby, for each silicate tetrahedron, the six O-O bonds employ 52% (5.61 electrons) of the valence electrons, while the four Si-O bonds employ 48% (5.12 electrons), rendering the O-O bond the most abundant bond in the Earth's crust. The isodesmic deconstruction of silica clusters reveals cooperative O-O bonding with an O-O bond dissociation energy of 4.4 kcal/mol. These unorthodox, long covalent bonds are rationalized by an excess of O 2 -O 2 bonding versus anti-bonding interactions within the valence molecular orbitals of the SiO unit (48 vs. 24) and the Si O ring (90 vs. 18). Within quartz silica, oxygen 2 orbitals contort and organize to avoid molecular orbital nodes, inducing the chirality of silica and resulting in Möbius aromatic Si O rings, the most prevalent form of aromaticity on Earth. This long covalent bond theory (LCBT) relocates one-third of Earth's valence electrons and indicates that non-canonical O-O bonds play a subtle, but crucial role in the structure and stability of Earth's most abundant material.