Chemisorption bondlength

In early structural studies of adsorbates on surfaces there was an implicit assumption that the surface provided a rigid chequer board of identical sites into which atoms or molecules were adsorbed, the only structural parameters of interest being the lateral registry and the adsorbate-substrate chemisorption bondlength. It was, of course, understood that the surface could modify the adsorbate species, most obviously through partial dissociation, but also in more subtle ways, because this is the whole... 

At the time that this survey of chemisorption bondlengths was undertaken, the database of molecular adsorption structures [139] was even more sparse, inadequate for any clear pattern to be established. More recently, we have returned to this problem through a detailed study of one specific chemisorption system, namely CO on Ni surfaces [142,143]. The objective was two-fold. First, by conducting PhD experimental structure determinations for different phases of CO on Ni(100) and Ni(lll) it was possible to obtain Ni—CO chemisorption bondlengths for 1-,... 

The basic finding was that for chemisorption bonds, as for those in inorganic materials generally, bondlengths, D, and bond order, n, appear to be related by a Pauling-like expression [141] between an adsorbate X and the metal surface atoms M of the type... 

While this question of a possible minority species in this surface reaction remains unresolved, one important aspect of the more complete PhD study is the determination of the chemisorption Ti— bondlengths to both the carboxylate (2.08 0.03 A) and hydroxyl (2.02 0.05 A) species, which turn out to be in excellent agreement with the values (2.08 and 2.01 A, respectively) for the one theoretical (DFT) calculation that considers this coadsorption situation explic-... 

---