Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with...
Transcript of Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with...
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
![Page 2: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/2.jpg)
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
Crystal structure considered known when atom positions knownvery precisely
![Page 3: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/3.jpg)
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
Crystal structure considered known when atom positions knownvery precisely
LaCoAl4Pmma a = 7.701, b = 4.082, c = 7.023 Å
La 2e (1/4 0 0.388) ….Co 2e (1/4 0 0.813) ….Al1 2a (0 0 0) ….Al2 2f (1/4 1/2 0.022) ….Al3 4f (0.061 1/2 0.708) ….
![Page 4: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/4.jpg)
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
Crystal structure considered known when atom positions knownvery precisely
X-ray diffraction data used for structure determination
reflection positions ––> cell size, space group symmetry
intensities ––> atom positions
![Page 5: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/5.jpg)
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
Crystal structure considered known when atom positions knownvery precisely
X-ray diffraction data used for structure determination
reflection positions ––> cell size, space group symmetry
intensities ––> atom positions
Thus precise lattice parameters & precise atom positionsdetermined in 2 separate steps
![Page 6: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/6.jpg)
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
Crystal structure considered known when atom positions knownvery precisely
X-ray diffraction data used for structure determination
reflection positions ––> cell size, space group symmetry
intensities ––> atom positions
Ihkl ~ |Fhkl|2 Fhkl = Σ ƒj e2πi (hxj + kyj + lzj)
![Page 7: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/7.jpg)
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Rietveld methodmethod for refinement of crystal structures
what does this mean?
Initial values of atom positions obtained during structure analysisrarely the most precise values – & closest to truth
Values must be refined - use least squares procedure to make smalladjustments in atom positions
![Page 8: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/8.jpg)
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Rietveld method
Previously:
Determine areas underall observed Bragg peaks
Use these intensities toget model for structure
Refine model on basis ofreflection intensities
Mostly single crystal intensities used, but same procedure used for “powder” patterns
![Page 9: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/9.jpg)
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Rietveld method
Problems wrt powder patterns:
Loss of information -
peak shape, width, tails
![Page 10: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/10.jpg)
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Rietveld method
Problems wrt powder patterns:
Loss of information -
peak shape, width tails
background
![Page 11: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/11.jpg)
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Rietveld method
Problems wrt powder patterns:
Loss of information -
peak shape, width tails
background
Peak overlap problems
![Page 12: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/12.jpg)
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Rietveld method
Problems wrt powder patterns:
Loss of information -
peak shape, width tails
background
Peak overlap problems
Other things:
Preferred orientation gives wrong intensities
What about multiple phase patterns?
![Page 13: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/13.jpg)
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Rietveld method
Uses every datum (yobs) collected, individually
Each yobs compared with a corresponding calculated value (ycalc)
Must be able to calculate ycalc
![Page 14: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/14.jpg)
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Rietveld method
Uses every datum (yobs)collected, individually
Each yobs compared with a corresponding calculated value (ycalc)
Must be able to calculate ycalc
Need models for all scattering effects - both Bragg peaks & backgrd
Models all involve parameters
Herein lies the complexity of the method
![Page 15: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/15.jpg)
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Rietveld method
Uses every datum (yobs)collected, individually
Each yobs compared with a corresponding calculated value (ycalc)
Must be able to calculate ycalc
Need models for all scattering effects - both Bragg peaks & backgrd
Models all involve parameters
Herein lies the complexity of the method
Change parameters according to the least squares criterion
Minimize R = Σ wi (yobs
– ycalc)2i i i
![Page 16: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/16.jpg)
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Rietveld method
Rietveld algorithms - 1966+
Development of automated diffractometry - early 1980s
Increased computing power
![Page 17: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/17.jpg)
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Rietveld method
Rietveld algorithms - 1966+
Development of automated diffractometry - early 1980s
Increased computing power
Rise of demand for information contained in peak shapes, background
crystallite sizemicrostressthermal motionstacking faultsamorphous contentother atomic disorder
![Page 18: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/18.jpg)
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Least squares
Simple example – straight line fit
What is best straight line to represent these data?
![Page 19: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/19.jpg)
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Simple example – straight line fit
What is best straight line to represent these data?
Minimize sum of squaresof these distances
R = Σ (yobs – ycalc)2
Least squares
i i i
![Page 20: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/20.jpg)
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Simple example – straight line fit
What is best straight line to represent these data?
Minimize sum of squaresof these distances
R = Σ (yobs – ycalc)2
ycalc values unknown except
y = mx + b (straight line)
Least squares
i i i
i
![Page 21: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/21.jpg)
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Simple example – straight line fit
What is best straight line to represent these data?
Minimize sum of squaresof these distances
R = Σ (yobs – ycalc)2
ycalc values unknown except
y = mx + b (straight line)
Least squares
i
Then
R = Σ (yobs – (mx + b))2
i
i
ii i i
![Page 22: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/22.jpg)
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Simple example – straight line fit
What is best straight line to represent these data?
Minimize sum of squaresof these distances
R = Σ (yobs – ycalc)2
ycalc values unknown except
y = mx + b (straight line)
Least squares
i
Then
R = Σ (yobs – (mx + b))2
Minimize R
∂R/∂m = ∂R/∂b = 0
–2Σ (yobs – (mx + b))x = 0
–2Σ (yobs – (mx + b)) = 0
i
i
ii i i
![Page 23: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/23.jpg)
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Simple example – straight line fit
Least squares
i
–2Σ (yobs – (mx + b))x = 0 Σ x yobs
= m Σ x2 + b Σ x
–2Σ (yobs – (mx + b)) = 0 Σ yobs
= m Σ x + b Σ 1
i
ii
ii i i ii
i i
![Page 24: Rietveld method - personal.ems.psu.eduryba/coursework/Rietveld/Rietveld-1.pdfEach yobs compared with a corresponding calculated value (ycalc) Must be able to calculate ycalc Need models](https://reader036.fdocuments.in/reader036/viewer/2022062509/60fad573a06514355b703031/html5/thumbnails/24.jpg)
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Simple example – straight line fit
Least squares
i
–2Σ (yobs – (mx + b))x = 0 Σ x yobs
= m Σ x2 + b Σ x
–2Σ (yobs – (mx + b)) = 0 Σ yobs
= m Σ x + b Σ 1
These are the normal equations
Insert data (x, y values) & solve for m, b
i
ii
ii i i ii
i i