TY - JOUR
T1 - Stoichiometry and local atomic arrangements in crystals
AU - Ellison, Adam J.G.
AU - Navrotsky, Alexandra
N1 - Funding Information:
This work was initiatedw ith the supporto f the U.S. Departmento f Energy, Grant DE FG0285 ER 13437. It was completedu nder the auspices of the U.S. Department of Energy, Division of Materials Sciences, Office of Basic Energy Sciences,u nderC ontractW -31-109-ENG-38.
PY - 1991/9
Y1 - 1991/9
N2 - Valence crystals have bulk stoichiometries that are electroneutral with respect to formal atomic valence, and structures in which cation sites are formed entirely by anions and vice versa. This description is shown to be equivalent to a set of stoichiometric and structural rules limiting local atomic configurations in valence crystals. Algebraic equivalents of these rules are used to derive a necessary mathematical link between bulk stoichiometry and local atomic arrangements in valence crystals. In the limit of no charge imbalances on anion sites, this link reduces to the electrostatic valence principle of Pauling. Numerical analysis shows that limits upon the coordination numbers of cations and anions severely restrict the number and type of local configurations that could ever be combined to form an electroneutral bulk stoichiometry, regardless of the valence of the anion or the magnitude of charge imbalances on anion sites.
AB - Valence crystals have bulk stoichiometries that are electroneutral with respect to formal atomic valence, and structures in which cation sites are formed entirely by anions and vice versa. This description is shown to be equivalent to a set of stoichiometric and structural rules limiting local atomic configurations in valence crystals. Algebraic equivalents of these rules are used to derive a necessary mathematical link between bulk stoichiometry and local atomic arrangements in valence crystals. In the limit of no charge imbalances on anion sites, this link reduces to the electrostatic valence principle of Pauling. Numerical analysis shows that limits upon the coordination numbers of cations and anions severely restrict the number and type of local configurations that could ever be combined to form an electroneutral bulk stoichiometry, regardless of the valence of the anion or the magnitude of charge imbalances on anion sites.
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U2 - 10.1016/0022-4596(91)90227-9
DO - 10.1016/0022-4596(91)90227-9
M3 - Article
AN - SCOPUS:44949270824
VL - 94
SP - 130
EP - 148
JO - Journal of Solid State Chemistry
JF - Journal of Solid State Chemistry
SN - 0022-4596
IS - 1
ER -