John F. Wager1,3, Douglas A. Keszler2 School of EECS1, Department of Chemistry2, Oregon State University; presenting author3 According to the atomic solid-state energy (SSE) scale, SSE, like electronegativity, is an attempt to account for a wide range of chemical properties of an element using a single, scalar quantity. SSE for a given element in a specified oxidation state corresponds to its average frontier orbital energy position with respect to the vacuum level. SSEs for most cations (anions) are positioned above (below) -4.5 eV with respect to the vacuum level. Hence, the energy -4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/-) or equivalently the standard hydrogen electrode energy, is an absolute energy reference for solid-state chemical bonding. The range of electron affinity, EA (for a cation) or ionization potential, IP (for an anion) is a measure of SSE variability. SSE variability assessment provides deep insight into the nature of the solid-state chemical bond since frontier orbital positioning depends strongly on the cation-anion interatomic distance. As the cation-anion interatomic distance decreases, the band gap increases, EA moves away from ε(+/-) toward the vacuum level, and IP moves away from ε(+/-) and away from the vacuum level. A molecular orbital picture of solid state bonding in a binary compound involves (see figure) (a) electronic charge transfer associated with ionic bonding, (b) frontier orbital alignment signaling termination of ionic bonding, and (c) electronic charge redistribution characteristic of polar covalent bonding.

Atomic solid state energy scale

253rd National Meeting (2017)

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