Procedure for structure analysis

Overview of strategy

What is needed

lattice parameters
reflection positions
space group
equipoint occupation
reflection intensities
positional parameters
Procedure for structure analysis
Overview of strategy

What is needed

lattice parameters
reflection positions
space group

done simultaneously
Procedure for structure analysis
Overview of strategy

What is needed

lattice parameters
reflection positions
space group

done simultaneously

need crystal system for size & shape of UC

some info on symmetry also acquired
Procedure for structure analysis
Overview of strategy

What is needed

lattice parameters
reflection positions
space group

done simultaneously

need crystal system for size & shape of UC

some info on symmetry also acquired

small no. reflections needed for crystal system

and approx. LPs
Procedure for structure analysis
Overview of strategy

What is needed

lattice parameters
reflection positions
space group

done simultaneously

need crystal system for size & shape of UC

some info on symmetry also acquired

small no. reflections needed for crystal system

and approx. LPs large no. for precise LPs
Examples for LP detn

Get a-value for each reflection

Which one is correct? or best?

Examples for LP detn

Depends upon 

Consider effect of expt'l error
on a-values at different s
Braggs' law says error in d
depends on error in sin 
Examples for LP detn

Braggs' law says error in d

depends on error in sin 
d eqn says error in a (cubic)
depends on error in d
d2 = a2/(h2 + k2 + l2)
Thus, error in a depends on
error in sin 
Precise LPs

Best a-value at  = 90°

extrapolate a-values vs. cos2 
Precise LPs

Best a-value at  = 90°

extrapolate a-values vs. cos2 
Precise LPs

Best a-value at  = 90°

extrapolate a-values vs. cos2 
Precise LPs

Another common extrapolation fcn -

Nelson-Riley fcn
Procedure for structure analysis
Overview of strategy

LPs & SG done simultaneously

need crystal system for size & shape of UC

some info on symmetry also acquired

systematic extinctions ––> Bravais lattice

glide planes, screw axes

space group - almost

ex: Imma (centric) ––– Im21a (non-centric)

get correct SG in final structure detn
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
atom sizes
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
atom sizes
properties (centric?)
isostructural materials (use databases)

Ex: Al9Co3Ce
do search on LPs
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
atom sizes
properties (centric?)
isostructural materials (use databases)

Ex: Al9Co3Ce
do search on LPs
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
atom sizes
properties (centric?)
isostructural materials (use databases)

Ex: Al9Co3Ce
do search on LPs

Ga9Co3Nd
(structure known)

only need to "refine"

Al9Co3Ce structure
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
atom sizes
properties (centric?)
isostructural materials (use databases)

2. Measure intensities of as many reflections as possible -

correct for LP, absorption
 Techniques for structure detn

1. Gather supplemental info

chemical structure
density = (# formula units/UC x form. wt.)/(No x UC volume)
atom sizes
properties (centric?)
isostructural materials (use databases)

2. Measure intensities of as many reflections as possible -

correct for LP, absorption

3. Determine atom positions

a. Patterson techniques
b. heavy atom method
 Techniques for structure detn

3. Determine atom positions

a. Patterson techniques
b. heavy atom method
 Techniques for structure detn

3. Determine atom positions

a. Patterson techniques
b. heavy atom method
c. isomorphous replacement,
anomalous scattering
 Techniques for structure detn

3. Determine atom positions

a. Patterson techniques
b. heavy atom method
c. isomorphous replacement,
anomalous scattering
d. direct methods

Unitary structure factors

 Techniques for structure detn

3. Determine atom positions

d. direct methods

Unitary structure factors

Example: center of symmetry

Additional symmetry elements give

other relationships
 Techniques for structure detn

4. Refine structure
adjust positional parameters to get best
agreement betwn Fobs & Fcalc

use least squares technique

FOM – the R factor

 Techniques for structure detn

4. Refine structure
adjust positional parameters to get best
agreement betwn Fobs & Fcalc

use least squares technique

FOM – the R factor

Include thermal parameters for each atom

 Techniques for structure detn

4. Refine structure

Include thermal parameters for each atom

or
 Techniques for structure detn

4. Refine structure

Include thermal parameters for each atom

or

For anisotropic vibration, thermal ellipsoid for

each atom
 Techniques for structure detn

Rietveld refinement

For powder diffraction data

Not a structure determination procedure

Whole pattern used

Need to model peak shapes

 Techniques for structure detn

Rietveld refinement

For powder diffraction data

Not a structure determination procedure

Whole pattern used

Need to model peak shapes

Many data, many parameters:

lattice params, backgrd curve coeffs,

positional params,temp factors, peak
shape params, texture factor, etc.
 Techniques for structure detn

Rietveld refinement