Structure Factors. How to get more than unit cell sizes from your diffraction data.

Transcription

1 Structure Factors How to get more than unit cell sizes from your diffraction data

2 Yet again expanding convenient concepts First concept introduced: Reflection from lattice planes - facilitates derivation of Bragg s law - explains the location of spots on the observed diffraction pattern Second concept introduced: Scattering from atoms, all the electron density was assumed to be concentrated in a lattice point (e.g., origin of the unit cell) - gave the correct locations for spots in the diffraction pattern But what about atoms that are located between lattice planes? - any atom can scatter an X-ray that hits it - what does this imply for the overall scattering amplitude?

3 toms between lattice planes toms between lattice planes will always scatter X-rays so that the resulting wave is partially out of phase with X-rays scattered from the lattice planes - the lattice planes can be envisioned as atoms located in the plane described Structure Determination by X-ray Crystallography, Ladd and Palmer, Plenum, 1994.

4 Description of a plane Point P can be described by the vector p, which is perpendicular to the plane LMN, or by the coordinates (X,Y,Z) - the intercept equation of the plane is given by X/a p +Y/b p +Z/c p = 1 - this can be rearranged to X cosχ + Y cosψ + Z cosω = p Structure Determination by X-ray Crystallography, Ladd and Palmer, Plenum, describes family of parallel planes that are located at distance p from 0

5 X cosχ + Y cosψ + Z cosω = p Path difference For plane O : p = d hkl ; a p = a/h; b p = b/k; c p = c/l cosχ = d hkl /(a/h); cosψ = d hkl /(b/k); cosω = d hkl /(c/l) For plane : p = d ; atom at (X, Y, Z ) dhkl dhkl d = X + Y a/h b/k d (hx + ky + lz )dhkl + Z d c/l = using fractional coordinates ccording to Bragg s law, the path difference between O and is δ = 2dsinθhkl = 2dhklsinθhkl(hx + ky + lz δ = λ(hx + ky + lz ) hkl )

6 We can describe a wave as Using wave equations instead W 0 = f cos(2πx/λ) or W 0 = f cos(ωt) where W 0 is the transverse displacement of a wave moving in the X direction, the maximum amplitude is f at t=0 and X=0 For other waves with a maximum at t=t n and X=X n, we can write W n = f n cos(2πx/λ - φ n ) where φ n = 2πX n /λ Two arbitrary waves of same frequency can then be represented as W 1 = f 1 cos(ωt - φ 1 ) = f 1 [cos(ωt) cos(φ 1 ) + sin(ωt) sin(φ 1 )] W 2 = f 2 cos(ωt - φ 2 ) = f 2 [cos(ωt) cos(φ 2 ) + sin(ωt) sin(φ 2 )] Sum: W = W 1 +W 2 = cos(ωt) ( f 1 cos(φ 1 )+ f 2 cos(φ 2 ))+sin(ωt) ( f 1 sin(φ 1 )+ f 2 sin(φ 2 ))

7 Wave equations continued We know that we can write any wave as W = F cos(ωt - φ) = F [cos(ωt) cos(φ) + sin(ωt) sin(φ)] Comparison with the equations on the last slide gives F cos(φ) = f 1 cos(φ 1 ) + f 2 cos(φ 2 ) F sin(φ) = f 1 sin(φ 1 ) + f 2 sin(φ 2 ) F can be calculated as F = [(f 1 cos(φ 1 ) + f 2 cos(φ 2 )) 2 + (f 1 sin(φ 1 ) + f 2 sin(φ 2 )) 2 ] 1/2

8 rgand diagrams Waves can be represented as vectors in an rgand diagram - represented with real and imaginary components - allows for straightforward wave addition - For any given wave, we can write F = F (cos(αt) + i sin(αt)) = F e iαt (compare to slide 9 of handout 6!) Crystal Structure nalysis for Chemists and Biologists, Glusker, Lewis and Rossi, VCH, 1994.

9 Wave addition using rgand diagrams ny number of waves can be added using an rgand diagram - For N waves, F cos( φ) - lternatively, we can write N = f cos( φ ); F sin( φ) = f sin( φ ) = 1 N = = 1 iφ iφ F f e = F e N = 1 Structure Determination by X-ray Crystallography, Ladd and Palmer, Plenum, 1994.

10 Phase difference From our treatment of path differences of waves scattered by arbitrary atoms, we obtained δ = λ( hx + ky + lz ) The corresponding phase difference can be written as φ = ( 2π / λ) δ = 2π ( hx + ky + lz ) This implies that our expression for F depends on the diffraction direction as described by the Miller indices hkl (or the diffraction angle, if you prefer)

11 Structure factors F should be more properly written as F(hkl) or F hkl to express its dependence on the diffraction angle There will be a unique F(hkl) corresponding to each reflection in a diffraction pattern - note and remember! that all atoms in a crystal contribute to every F(hkl)! F(hkl) is called the structure factor for the (hkl) reflection Can be broken down in its real and imaginary components F( hkl ) = ( hkl) + ib( hkl) N = = 1 ( hkl) f cos(2π ( hx + ky + lz where )) N = = 1 B ( hkl) f sin(2π ( hx + ky + lz ))

12 tomic scattering factors The individual atomic components, f, are called atomic scattering factors - depend on nature of atom, direction of scattering, and X-ray wavelength - provide a measure of how efficiently an atom scatters X-rays compared to an electron - usually written as f, although they should be written as f,θ,λ - listed as a function of sin(φ)/λ for each atom in the International Tables - maximum value of f is Z, the number of electrons of the th atom

13 Intensity and structure factors We cannot measure structure factors, instead, we will measure the intensity of diffracted beams The phase is given by I( hkl) F( hkl) F*( hkl) 2 2 F ( hkl) = ( hkl) + B tan( φ) = B( hkl) / ( hkl) F *( hkl) = F( hkl) e ( hkl) Problem: We lose the phase information when measuring intensities! 2 iφ

14 Factors between I and F There are several factors between I and F that will change the measured intensity: - thermal vibration of the atoms: exp[-b (sin 2 (θ)/λ 2 ] - Lorentz factor, for normal 4 circle diffractometers: 1/sin(2θ) - absorption: e -µt, where µ is the linear absorption coefficient and t the thickness of the specimen - polarization: p = (1+cos 2 (2θ))/2 - scale factor

15 Thermal vibration Thermal vibration smears out the electron cloud surrounding an atom - we see time average over all configurations - displacement of atoms leads to slight phase difference for atoms in neighboring unit cells - f = f 0 exp[-b (sin 2 (θ)/λ 2 ] - B = π u 2 - u is the mean square amplitude of displacement

16 Systematic absences Some reflections will be systematically absent from your diffraction pattern These absences are a result of - lattice centering - glide planes - screw axes Note that simple rotations and mirror planes to not give systematic absences! Space groups can be assigned based on systematic absences

17 Structure Determination by X-ray Crystallography, Ladd and Palmer, Plenum, Systematic absences (2)