结构化学2.pptVIP

All M.C. Escher works (c) Cordon Art-Baarn-the Netherlands.All rights reserved. How do we describe crystalline solids ？— Lattice 2D example – Square lattice (sodium chloride, NaCl) Choice of origin is arbitrary - lattice points need not be atoms - but unit cell size should always be the same. This is also a unit cell - it doesn’t matter if you start from Na or Cl - or if you don’t start from an atom This is NOT a unit cell even though they are all the same - empty space is not allowed! In 2D, this IS a unit cellIn 3D, it is NOT Definitions1. The unit cell “The smallest repeat unit of a crystal structure, in 3D, which shows the full symmetry of the structure” All planes in a set are identical The planes are “imaginary” The perpendicular distance between pairs of adjacent planes is the d-spacing Need to label planes to be able to identify them Plane perpendicular to y cuts at ?, 1, ? ? (0 1 0) plane d-spacing formula For orthogonal crystal systems (i.e. ?=?=?=90?) :- A cubic crystal has a=5.2 ? (=0.52nm). Calculate the d-spacing of the (1 1 0) plane Unit cell symmetries - cubic 4 fold rotation axes (passing through pairs of opposite face centers, parallel to cell axes) TOTAL = 3 Unit cell symmetries - cubic 4 fold rotation axes TOTAL = 3 Close packed structures - metals Most efficient way of packing equal sized spheres. In 2D, have close packed layers Two main stacking sequences: Two main stacking sequences: Let’s assume the second layer is B (red). What about the third layer? Two possibilities: (1) Can have A position again (blue). This leads to the regular sequence …ABABABA….. Hexagonal close packing (hcp) (2) Can have layer in C position, followed by the same repeat, to give …ABCABCABC… Cubic close packing (ccp) No matter what type of packing, the coordination number of each equal size sphere is always 12 ccp = fcc ? Lecture 1: Introduction Radius ratio rules Rationalisation for octahedral coordination: R= radius of large ion, r=radius