A study of the arsenic, black phosphorus, and other structures derived from rock salt by bond-breaking processes. II. Band structure calculations and the importance of the g a u c h e effect

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Abstract
Band structure calculations based on the extended Hückel method order energetically the 36 arsenic-like structures having the NaCl size unit cell in a way which is compatible with the observed crystal structures. Black phosphorus is the most stable of the 36, and the arsenic layer type is number seven. Energy differences among these structures can be explained by different energetic contributions from syn-, gauche, and anti-arrangements, of both bonded and nonbonded pairs of atoms, and by a destabilization accompanying small bond angles. The order of stability is gauche ≳ anti ≳syn. Lone pair repulsions are important in determining the total energy, but play only a minor role in the relative energies of these structures. The energies ascribed to all these local geometries are compatible with molecular orbital calculations on small molecules and with observed molecular conformations described by the ’’gauche effect.’’

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