Wiberg-type atomic valence formulae for diatomic electron-pair bonds and antibonds

2009 ◽  
Vol 897 (1-3) ◽  
pp. 83-85
Author(s):  
Richard D. Harcourt
1996 ◽  
Vol 52 (1) ◽  
pp. 7-15 ◽  
Author(s):  
X. Wang ◽  
F. Liebau

In the present bond-valence concept the bond-valence parameter ro is treated as constant for a given pair of atoms, and it is assumed that the bond valence sij is a function of the corresponding bond length Dij , and that the atomic valence is an integer equal to the formal oxidation number for Vi derived from stoichiometry. However, from a statistical analysis of 76 [SbIIIS n ] and 14 [SbIIISe n ] polyhedra in experimentally determined structures, it is shown that for SbIII—X bonds (X = S, Se), ro is correlated with {\bar \alpha} i , the average of the X—Sb—X angles between the three shortest Sb—X bonds. This is interpreted as a consequence of a progressive retraction of the 5s lone-electron pair from the SbIII nucleus, which can be considered as continuous change of the actual atomic valence act Vi of Sb from +3 towards +5. A procedure is derived to calculate an effective atomic valence eff Vi of SbIII from the geometry, {\bar \alpha} i and Dij , of the [SbIII Xn ] polyhedra, which approximates act Vi and is a better description of the actual valence state of SbIII than the formal valence for Vi . Calculated eff V SbIII are found to vary between +2.88 and +3.80 v.u. for [SbIIIS n ] and between +2.98 and +3.88 v.u. for [SbIIISe n ] polyhedra. It is suggested that a corresponding modification of the present bond-valence concept is also required for other cations with lone-electron pairs.


1931 ◽  
Vol 37 (9) ◽  
pp. 1177-1178 ◽  
Author(s):  
Maurice L. Huggins
Keyword(s):  

2006 ◽  
Vol 3 (6) ◽  
pp. 457 ◽  
Author(s):  
Richard D. Harcourt ◽  
Thomas M. Klapötke

Environmental Context. N2O5 is an important nitrogen reservoir in polar stratospheric clouds found in Antarctica and involved with the ozone hole. Here we provide valence bond representations for the gas-phase formation and decomposition of this molecule. Abstract. Qualitative valence bond considerations are used to suggest how electronic reorganization could proceed for (a) the formation of N2O5 via the reactions NO2 + O3 → NO3 + O2, and NO2 + NO3 → N2O5, and (b) the thermal decomposition of N2O5 via the following sets of reactions: (i) N2O5 → NO2 + NO3, 2NO3 → O2NOONO2 → 2NO2 + O2; (ii) NO2 + NO3 → ONOONO2 → NO + O2 + NO2, NO + NO3 → 2NO2. Increased-valence structures, which possess one-electron bonds and fractional electron-pair bonds as well as 'normal' electron-pair bonds, are used to represent the electronic structures of the molecules.


1992 ◽  
Vol 114 (20) ◽  
pp. 7861-7866 ◽  
Author(s):  
Sason Shaik ◽  
Philippe Maitre ◽  
Gjergji Sini ◽  
Philippe C. Hiberty

2009 ◽  
Vol 65 (6) ◽  
pp. 684-693 ◽  
Author(s):  
I. David Brown

The differences between Wang and Liebau's [Wang & Liebau (2007). Acta Cryst. B63, 216–228] stoichiometric valence (atomic valence) and structural valence (bond-valence sum) observed in Sn2+ and other lone-pair cation oxycomplexes arises from their use of the Brese & O'Keeffe bond-valence parameters which are based on the assumption that the bond-valence parameter b = 0.37 Å applies to all bond types. According to the theory of the bond-valence model, the bond-valence sum is necessarily equal to the ionic charge, implying that in the Wang and Liebau model the ionic charges are equal to the structural valence. If charges are chosen equal to the stoichiometric valence, the bond-valence parameters for Sn2+—O bonds are R 0 = 1.859 Å, b = 0.55 Å. While both models are theoretically valid, only the standard model relates bond valences to the concept of atomic valence. Wang and Liebau's suggestion that cation–lone-pair bonds make a significant contribution to the valence sums is confirmed, but such bonds cannot account for the full difference between the stoichiometric and structural valences because they are present in only a few compounds.


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