Crystal Structure from
Powder Diffraction data
a feasible way
Prof. Dr. Alexandre Cuin
Chemistry Department – UFJF
Juiz de Fora – Minas Gerais -
Brazil
Crystal Structure from Powder
Diffraction data
Experimental Section Data Processing
Main sources, Equipments, Detectors… “Indexing” --> find initial cell parameters
Source – Optics – Sample – Optics - Detector Intensity extraction algorithms
How do I choose the appropriate instrument?
How do I set the best parameters? LeBail algorithms Pawley method
Sample preparation
The measurement cannot be better than the sample!
Garbage in ---> Garbage out!
Systematic absences
Space group assignment
Crystal Structure from Powder
Diffraction data
Data Processing (cont) Means: find the correct “x y z”
coordinates of each inside the unit cell
1) Data collection – Full range has been done
Structure Solution 2) Lattice parameters are know from indexing routines;
3) Space group, lattice parameters, and some optical parameters
have been refined (unless good approximation);
1) Reciprocal Space method;
Structure Solution
Two main approaches
2) Real Space technique;
Crystal Structure from Powder
Diffraction data
Data Processing (cont)
Structure Solution On single crystal method the crystallographic model has
been built from experimental data while on “Powder
Diffraction” the model is built using ancillary information. If
the crystallographic model is appropriate, calculated data
fit on experimental ones.
Grid Search
Monte Carlo
Real Space Techniques
Genetic Algorithms
Simulated annealing (+Monte Carlo)
Crystal Structure from Powder
Diffraction data
Data Processing (cont)
Structure Solution
Real Space Techniques
Powder diffraction do not allow using Independent atom model… exception: heavy atoms
Strategies to build crystallographic model for Powder Diffraction analysis
Z_matrix
Independent atom – only for heavy atoms
Cartesian coordinates
Geometrical Cartesian coordinates
Cartesian coordinates using ‘Smile (to make cry)’
Crystal Structure from Powder
Diffraction data
Data Processing (cont) Refinement by Rietveld method
A decent starting model MUST be available
The final SDPD routine is always the Rieveld method approach
Hugo M. Rietveld (7 March 1932 in The Hague) is a Dutch crystallographer and one of
the most prominent crystallographers of the 20th century. He is famous for his invention
of the Rietveld refinement method, which is used for the characterisation of crystalline
materials from powder diffraction data. The Rietveld refinement uses a least squares
approach to refine a theoretical line profile (calculated from a known or postulated
crystal structure) until it matches the measured profile. The introduction of this
technique was a significant step forward in the diffraction analysis of powder samples.
“by wikipedia”
Crystal Structure from Powder
Diffraction data
Computer programs for the graphic representation of
Drawing structures molecular and crystallographic models
Shakal program
By Egbert Keller
Kristallographisches Institut der Universität
Hebelstr. 25 / D-79104 Freiburg / Germany
Schakal : an abbreviation for the two
germanic words SCHAttiert KALotten
[=shaded cups; shaded space-filling
models].
Mercury 3.5.1 (Build RC5)
Copyright CCDC 2001-2014
[email protected] http://www.ccdc.cam.ac.uk/mercury/
Quantitative Phase Analysis
The Rietveld Method for a Quantitative Phase Analysis (QPA)
Building and Optimization of a diffraction pattern model of a polyphasic
polycrystalline mixture
Building and Optimization of a diffraction pattern model of each single
crystal phase present in the mixture
The whole diffraction pattern of the mixture is the “weighted” sum of
the patterns of each single phase (and of a background)
Determination of the weight fractions of the crystalline phases within
the mixture using the refined scale factors
Crystal Structure from Powder
Diffraction data
Origen of Powder Diffraction Patterns X rays Diffraction on Single-Crystal
Crystal Structure from Powder
Diffraction data
X rays Diffraction on Single-Crystal
Origen of Powder Diffraction Patterns
Crystal Structure from Powder
Diffraction data
The rings are generated by a large number of randomly crystallites
Crystal Structure from Powder
Diffraction data
Crystal Structure from Powder
Diffraction data
Each reflection has:
position, intensity and shape
250,000
200,000
150,000
100,000
50,000
-50,000
5 10 15 20 25 30
Crystal Structure from Powder
Diffraction data
Crystal Structure from Powder
Diffraction data
250,000
200,000
Two related values:
150,000
‘d’ spacing
100,000 Angle: 2th
50,000
0 What is the relationship
of d and 2th?
-50,000
What is the relationship
these values with cell?
5 10 15 20
Crystal Structure from Powder
Diffraction data
What is the relationship of d and 2th?
Crystal Structure from Powder
Diffraction data
What is the relationship of 2th (d spacing) values with cell parameters?
Lattices, planes and directions
Bi-dimensional lattices
Tri-dimensional
lattices
Crystal Structure from Powder
A.Cuin
Diffraction data
Reciprocal lattice…
Crystal Structure from Powder
Diffraction data
What is the relationship of 2th (d spacing)
Crystal Cell parameters
values with cell parameters?
system
Cubic a = b = c and α = β = γ = 90o;
Hexagonal a=b≠c; α=β=90o and γ = 120o;
Trigonal a = b = c and α = β = γ ;
Orthorhombic a ≠ b ≠ c and α = β = γ = 90o;
Monoclinic a ≠ b ≠ c; α = γ = 90o; and β≠ 90o
Triclinic a ≠ b ≠ c and α ≠ β ≠ γ ≠ 90o;
Crystalline systems
Crystal Structure from Powder
Diffraction data
The reciprocal lattices are 1/(dhkl)2…
dhkl
2θ
