Xraydiffractionstructualanalysis.pptVIP

Intensities of diffraction spots and structural factor I (hkl) ? | F(hkl) |2 (meaning that F(hkl) is not directly obtainable from diffraction data) Observed structural factor The phase problem F(hkl) = A(hkl) + iB(hkl) (i = √?1 ) |F |2 = (A + iB)(A?iB) = A2 + B2 (To have F (hkl) value, one must know A and B individually.) Effect of thermal vibration F(hkl) = ? fj exp[2?i(hxj + kyj + lzj )]exp[-Bj(sin?/?)2] j Bj, temperature factor for atom j. When there is an inversion center at 0, 0, 0, F(hkl) = ? fjexp[2?i(hxj + kyj + lzj)] = ? fj cos2? (hxj + kyj + lzj) + i ? fj sin2? (hxj + kyj + lzj) Structure factor of centrosymmetric crystal If there is an atom at xj, yj, zj, there must be another same atom at ?xj, ?yj, ?z. Therefore, F(hkl) = ? fj [cos2? (hxj + kyj + lzj) + cos2? (?hxj ?kyj ?lzj)] + i ? fj [sin2? (hxj + kyj + lzj) + sin2? (?hxj ? kyj ? lzj)] Since cos (??) = cos ?, but sin (??) = ?sin ? F(hkl) = 2? fj cos2? (hxj + kyj + lzj) It is a real number! Friedel’s law F(hkl) = A + iB F(hkl) = A ? iB Therefore, |F(hkl)|2 = A2 + B2 And |F(hkl)|2 = A2 + B2 The two planes, hkl and hkl, give the same intensities, and the diffraction pattern has a center of symmetry, whether the crystal has or not. Laue groups According to Fridel’s law, diffraction pattern for crystal having point group 4 is the same in intensity as that of 4/m. For tetragonal crystal system, a Laue group 4/m for point groups 4, 4 and 4/m. There are 11 Laue groups for the 32 point groups of 7 crystal systems Table of crystallographic point groups Calculated structure factor F(hkl) of NaCl NaCl, face centered cubic crystal system with Na+ at 0, 0, 0; 1 2 1 2 , 0; , 1 2 1 2 , 0, ; 1 2 1 2 , 0, Cl? at 1 2 0, 0; , 0, 0; 1 2 1 2 0, 0, 1 2 1 2 , , 1 2 ; F (hkl) = f Na+ (exp[2?i(0)] + exp[ ] + exp [ ] + exp [ ]) 2?i(h + k) 2 2?i(h + l) 2 2?i(k + l)