Bond lengths and bond valences of ions bonded to oxygen: their variability in inorganic crystals

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dc.contributor.authorGagné, Olivier C.
dc.contributor.examiningcommitteeHalden, Norman (Geological Sciences) Kroeker, Scott (Chemistry) Calas, Georges (Université Pierre et Marie Curie)en_US
dc.contributor.supervisorHawthorne, Frank C. (Geological Sciences)en_US
dc.date.accessioned2016-09-12T22:33:19Z
dc.date.available2016-09-12T22:33:19Z
dc.date.issued2015-10-01en_US
dc.date.issued2016-08-01en_US
dc.degree.disciplineGeological Sciencesen_US
dc.degree.levelDoctor of Philosophy (Ph.D.)en_US
dc.description.abstractA large amount of information concerning interatomic distances in the solid state is available, but little has been done in recent times to comprehensively filter, summarize and analyze this information. Here, I examine the distribution of bond lengths for 135 ions bonded to oxygen, using 180,331 bond lengths extracted from 9367 refined crystal structures collected from the Inorganic Crystal Structure Database (ICSD). The data are used to evaluate the parameterization of the bond-length—bond-valence relation of the bond-valence model. Published bond-valence parameters for 135 cations bonded to oxygen, and the various methods used in their derivation, are evaluated. New equations to model the relation are tested and the common form of the equation is found to be satisfactory. A new method (the Generalized Reduced Gradient Method, GRG method) is used to derive new bond-valence parameters for 135 cations bonded to oxygen, leading to significant improvements in fit for many of the ions. The improved parameterization is used to gain crystal-chemical insight into the milarite structure. A literature review of 350+ published compositions is done to review the end-members of the milarite group and to identify compositions that should have been described as distinct minerals species. The a priori bond-valences are calculated for minerals of this structure, and are used to examine the controls of bond topology on site occupancy, notably by localizing the major source of strain of the structure (the B site). Examination of the compositions of all known milarite-group minerals shows that compositions with a fully occupied B site are less common than those with a vacant B site, in accord with the idea that the B site is a local region of high strain in the structure. The bond-length distributions for the ions of the alkali and alkaline-earth metal families are examined. Variations in mean bond-lengths are only partly explained by the distortion theorem of the bond-valence model. I have found that bond length also correlates with the amount of vibrational displacement of the constituent ions. The validity of some uncommon coordination numbers, e.g., [3]-coordinated Li+, [3]-coordinated Be2+, is confirmed.en_US
dc.description.noteOctober 2016en_US
dc.identifier.citationGagné, O.C. & Hawthorne, F.C. (2015). Comprehensive derivation of bond-valence parameters for ion pairs involving oxygen. Acta Crystallographica, B71, 562-578en_US
dc.identifier.citationGagné, O.C. & Hawthorne, F.C. (2016). Bond-length distributions for ions bonded to oxygen: Alkali and alkaline-earth metals. Acta Crystallographica, B72, 602-625en_US
dc.identifier.urihttp://hdl.handle.net/1993/31697
dc.language.isoengen_US
dc.publisherActa Crystallographica Ben_US
dc.publisherActa Crystallographica Ben_US
dc.rightsopen accessen_US
dc.subjectBond lengthen_US
dc.subjectBond valenceen_US
dc.subjectMilariteen_US
dc.subjectCoordination numberen_US
dc.subjectAlkali metalen_US
dc.subjectAlkaline-earth metalen_US
dc.subjectStructural strainen_US
dc.subjectMean bond-lengthen_US
dc.subjectBond-valence modelen_US
dc.titleBond lengths and bond valences of ions bonded to oxygen: their variability in inorganic crystalsen_US
dc.typedoctoral thesisen_US
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