By D. Michael P. Mingos
Content material: Bond length-bond valence relationships, with specific connection with polyoxometalate chemistry / K.H. Tytko -- A bond version for polyoxometalate ions composed of MO6 octahedra (MOk polyhedraa with okay > four) / K.H. Tytko -- Bonding and cost distribution in isopolyoxometalate ions and suitable oxides -- a bond valence process / K.H. Tytko
Read or Download Bonding and Charge Distribution in Polyoxometalates: A Bond Valence Approach (Structure and Bonding, Volume 93), 1st Edition PDF
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Extra info for Bonding and Charge Distribution in Polyoxometalates: A Bond Valence Approach (Structure and Bonding, Volume 93), 1st Edition
001 [23, 24, 27, 61, 62]), an erroneous position of a bridging O atom between two to six M atoms leads to errors for the respective M-O bond lengths which strongly depend on each other. In this way the effects of the bond lengths errors in question are largely compensated. Unsuitable structural data have been identified (and rejected) by the large contribution of the respective structures to the average error square for the sum of the bond valences about the M atoms (with use of optimally chosen B and do values, resulting in a minimal eu according to Eq.
The approach in the literature [9, 16, 17, 19, 32] to consider the single MOk polyhedra separately even if they are part of a polymeric species and in this case dependent on each other does not allow an adequate identification of erroneous structural data. This problem is most obvious in the case of structures containing only few (two) crystallographically independent MOk polyhedra which are present in widely different numbers. The error (difference of Y~si as against ~ ~q--1(~'~,Si))) of the MOk polyhedra forming the majority has to be compensate~[ by a correspondingly larger error of the MOk polyhedra forming the minority.
U. Hence Eq. (la) gives a somewhat better description of the structural data than Eq. (lb). I n t r o d u c t i o n of a third adjustable parameter into Eqs. , according to s = 10(d;-d)/S'+a/d or s = [ d o / ( d - y)] N' , (lla, lIb) respectively, led for the case o f Eq. (1 la) to no further i m p r o v e m e n t of az and for the case o f Eq. , the value which was also obtained with Eqs. (la) and ( l l a ) ; the agreement of the three az's is to within three places o f decimals. u. 0%) is virtually solely due to b o n d length errors in the structures (compare Sects.