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Semiconductor glasses exhibit many unique optical and electronic anomalies.We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508(2010)) in which several of these anomalies arise from deep midgap electronicstates residing on high-strain regions intrinsic to the activated transportabove the glass transition. Here we demonstrate at the molecular level how thisscenario is realized in an important class of semiconductor glasses, namelychalcogen and pnictogen containing alloys. Both the glass itself and theintrinsic electronic midgap states emerge as a result of the formation of anetwork composed of $\sigma$-bonded atomic $p$-orbitals that are only weaklyhybridized. Despite a large number of weak bonds, these $pp\sigma$-networks arestable with respect to competing types of bonding, while exhibiting a highdegree of structural degeneracy. The stability is rationalized with the help ofa hereby proposed structural model, by which $pp\sigma$-networks aresymmetry-broken and distorted versions of a high symmetry structure. The latterstructure exhibits exact octahedral coordination and is fullycovalently-bonded. The present approach provides a microscopic route to a fullyconsistent description of the electronic and structural excitations in vitreoussemiconductors.

Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the $pp\sigma$-network