Pauing的 规则(英文)学习指导.docVIP

Pauling’s Rules In 1929 Linus Pauling [J. Am. Chem. Soc.?51, 1010 (1929)] stated five principles which could be used to determine the structures of complex ionic/covalent crystals.? These ideas have since been refined and quantified but they remain an amazingly useful guide to understanding the crystal structures.? They serve as the outline for a discussion of structure determining forces in crystals where ionic interactions dominate.? (1) A coordinated polyhedron of anions is formed about each cation, the cation-anion distance determined by the sum of ionic radii and the coordination number by the radius ratio. Although many different sets of ionic radii have been created over the years, almost everyone currently uses the ionic radii set first derived by Shannon and Prewitt (R.D. Shannon and C.T. Prewitt,?Acta Cryst.?B25, 925-945 (1969)) and later refined by Shannon (R.D. Shannon,?Acta Cryst.?A32, 751-767 (1976)).? They actually derived two sets of ionic radii, one set is called the crystal radii (CR) was derived to best approximate experimentally determined ionic radii, the second set called ionic radii (IR) have values which approximate the cation and anion sizes found in the older tables of ionic radii.? The two sets are related by the following equations: for cations??????? IR = CR - 14 pm?for anions???????? IR = CR + 14 pm Below I outline several trends in the crystal radii values of Shannon. (A) As we move down a group in the periodic table, the CR increases. The exception to this is going from the 4d to 5d series among the transition metals (due to the lanthanide contraction). For example, consider the crystal radii (in angstroms) of the following elements in 6-fold coordination. ????????? Al3+?????? 0.675?????????? Ga3+??????0.760?????????? In3+?????? 0.940?????????? Tl3+???????1.025 ????????? Ti4+?????? 0.745?????????? Zr4+?????? 0.86?????????? Hf4+???????0.85 (B) As you increase the oxidation state, cations get smaller. For example, (once again in 6