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231223s2007 xx ||||| 00| ||eng c |
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|a (NLM)17063478
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|a DE-627
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|a eng
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|a Landis, C R
|e verfasserin
|4 aut
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|a Valence and extra-valence orbitals in main group and transition metal bonding
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|c 2007
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|a Text
|b txt
|2 rdacontent
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|a ohne Hilfsmittel zu benutzen
|b n
|2 rdamedia
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|a Band
|b nc
|2 rdacarrier
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|a Date Completed 25.01.2007
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|a Date Revised 12.12.2006
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|a published: Print
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|a Citation Status PubMed-not-MEDLINE
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|a Copyright (c) 2006 Wiley Periodicals, Inc.
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|a 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 character). The results provide a quantitative measure of superiority both for the standard NAO evaluation of atomic charges as well as the general 3c/4e (A: B-C<-->A-B :C resonance) picture of main- and transition-group hypervalency
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|a Journal Article
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|a Weinhold, F
|e verfasserin
|4 aut
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|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 28(2007), 1 vom: 15. Jan., Seite 198-203
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
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| 773 |
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|g volume:28
|g year:2007
|g number:1
|g day:15
|g month:01
|g pages:198-203
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|a AR
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|d 28
|j 2007
|e 1
|b 15
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|h 198-203
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