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Valence and Extra-valence Orbitals in Main Group and Transition Metal Bonding by C. R. Landis; F. Weinhold is a Chemistry article available to read on EtoBox.

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## Abstract We address the issue first raised by Maseras and Morokuma with regard to the questionable treatment of empty p‐orbitals in the algorithm for natural atomic/bond orbitals (NAOs, NBOs) and associated natural population analysis. We quantify this issue in terms of the numerical error (root‐mean‐square density deviation) resulting from the two alternative treatments of empty p‐sets, leading to distinct NAOs, atomic charges, and idealized Lewis structural representations. Computational application of this criterion to a broad spectrum of main group and transition group species (employing both single‐ and multi‐structure resonance models) reveals the interesting general pattern of (i) relatively insignificant differences for normal‐valent species, where a single resonance structure is usually adequate, but (ii) clear superiority of the standard NAO algorithm for hypervalent species, where multi‐resonance character is pronounced. These comparisons show how the divisive issue of “valence shell expansion” in transition metal bonding is deeply linked to competing conceptual models of hypervalency (viz., “p‐orbital participation” in skeletal hybridization vs. 3c/4e resonance chara

Who reads Valence and Extra-valence Orbitals in Main Group and Transition Metal Bonding?

Author

C. R. Landis; F. Weinhold

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); John Wiley & Sons Inc.; Wiley (ISSN 0192-8651)

Published

2006

Language

EN

Field

Chemistry (Physical Sciences)