Chemistry 4000/5000/6000

Multiplicity of powder lines

o The d spacing formulae involve squares of the Miller indices. This has a consequence for the observed multiplicity of lines with identical d values. Consider first the cubic crystal system.
h k l 1 0 0 0 1 0 0 0 1 2 0 0 0 2 0 0 0 2 {100} 6 multiplicity h k l 1 1 0 0 1 1 1 0 1 2 1 0 1 2 0 2 2 0 0 2 1 0 1 2 multiplicity h k l 1 1 1 2 1 1 1 2 1 1 1 2 2 2 1 2 1 2 1 2 2 2 2 2 {111} 8 multiplicity h k l multiplicity

Part 3 - Introduction to X-rays, their generation and interaction with matter

0 2 2 2 0 1 1 0 2 2 0 2 {110} 12

Chemical Crystallography

Sample problem
1. Calculate and d values for the first eight lines in the X-ray powder pattern, using Cu K radiation (1.54184 ), of a primitive cubic substance with a = 5.00. What is the multiplicity of each line? Also, calculate the value of (h2 + k2 + l2) for each reflection. Miller {100} {110} {111} {200} {210} { } {211} {220} {221} {300} {310}
1.

Sample problem
Calculate and d values for the first eight lines in the X-ray powder pattern, using Cu K radiation (1.54184 ), of a primitive cubic substance with a = 5.00. What is the multiplicity of each line? Also, calculate the value of (h2 + k2 + l2) for each reflection.

= 2d sin

1 h2 + k 2 + l 2 = d2 a2

a = 5.00

h2+k2+l2 1 2 3 4 5 6 8 9 9 10

D() 5.00 3.54 2.87 2.50 2.24 2.04 1.79 1.67 1.67 1.58

8.87 12.6 15.5 17.6 20.2 22.2 25.5 27.5 27.5 29.2

multiplicity 6 12 8 6 12 8 12 8 6 12

Powder X-ray Diffractometers (1): Systematic Absences

o o Instead of a strip of film to collect the diffraction data, a radiation counter is used. The counter may be of the scintillation counter type, in which the impinging X-ray causes a photon emission at a phosphor, which is then detected optically this type must be moved with 2 (located on a suitable mechanical arm) Alternatively a fixed area detector is used (measures the whole diffraction pattern in one go.) The geometry is highly reminiscent of the Debye-Scherrer camera, with the sample contained in a glass or quartz capillary at the middle of the device. The detectors collect both geometric and intensity data under computer data collection control. Output is to a file of 2 vs. intensity or on older instruments to a strip chart recorder.

Powder Diffractometer with Scintillation Detector

o o o

Xray source

Detector

Sample mount A typical modern powder diffractomter (PANalytical brand) Detail view of similar instrument

Powder Diffractometer with Area Detector

o Detector o o o

The Powder Pattern

The result is a printout of intensity versus angle. A typical output of such a device is shown The example is that of metallic nickel, which is face centred cubic with a = 3.524 . This powder pattern can be compared to the film produced from an equivalent measurement performed with a Debye-Scherrer camera, shown below. For each line in the film, there is a peak in the printout. The intensity of the peaks is much easier to discern than would be the case by comparing faint and bright lines in the photographic film. The hump at the origin is leakage past the beam stop that is used to collect the direct beam and prevent this strong X-ray beam from destroying the highly sensitive counter.

o Sample mount Xray source o

o Probably a sample heating (or cooling) device

Systematically Absent Reflections

o o There are a large, but finite number of possible reflections from any given diffraction experiment. From the d-spacing formulae, it should be obvious that low symmetry crystals give rise to far more reflections with different d-spacing, than do high symmetry cells like the cubic system illustrated in the powder pattern of Ni. (i.e. where the multiplicity is low, there will be more lines of lower absolute intensity.) But as we already saw when looking at the film data in the last lecture, not all Miller indices always appear in a diffraction pattern. Why is this? Indeed, for all seven crystal systems, it is observed that within the set of possible reflections obtained from a consideration of the Miller indices and the d-spacing formulae, certain reflections are entirely missing or of anomalously low intensity. These are called systematically absent reflections or lattice extinctions. o o

Occurrence of systematic absences

Systematic absences depend on the space group of the unit cell. We can distinguish two causes: Non-primitive Bravais lattice types (i.e. F, C, I & R) Translational symmetry Non-primitive lattices: the example of body-centring The alpha-iron lattice is body centred. Remember from your General Chemistry course that very, very few metals adopt a primitive crystal lattice, because it does not favour closest packing of atoms. H However, for f the th sake k of f thi this llecture t Ih have artificially tifi i ll created t d a model d l of f iiron th that t iis primitive i iti cubic, using the metallic radius of 1.24 . This requires a cell with dimensions a = 2.48 and one Fe atom per unit cell. The true body-centred cubic metallic lattice for iron has a = 2.8665 with 2 Fe per cell. Consider the powder X-ray diffraction patterns for these two models of iron, using Cu K radiation ( = 1.540562 ):

o o

o o

o o o o

Non-primitive lattice
Absent (missing) reflections in the actual c-I Fe lattice
Intensity (%) 100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100 110 2 () 120 1,1,1 (65.03,17.7) 2,1,0 (87.89,18.3) 1,0,0 (36.16,100.0) Intensity (%) 100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100 110 2,0,0 (65.02,13.0) 2,1,1 (82.33,22.0) 2,2,0 (98.94,6.7) 3,1,0 (116.37,11.2) 2 () 120 1,1,0 (44.67,100.0)

Checking the powder pattern

1 d hkl
o o
2

4sin 2

h2 + k 2 + l 2 a2

Test the (1 1 0) reflection, which is common to both patterns For Primitive cubic iron: sin =

1,1,0 (52.07,60.4)

1.540562 12 + 12 + 02 ; = 26.0; 2 = 52.0 4 2.482 2

52.07 in cc-P lattice

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For BCC iron:

sin =

1.540562 12 + 12 + 02 ; = 22.3; 2 = 44.6 4 2.86652 44 67 in c44.67 c-I Fe lattice

Iron in a Primitive Cubic cell

Iron in the actual Cubic-I cell

The reciprocal nature of Braggs law implies that the larger a unit cell parameter,the smaller the corresponding value of 2 Why is the pattern calibrated in two times theta, why not choose theta itself? There is no easy answer to this question, and crystallographic data comes in both versions! 2 is often the actual angle between the detector and the incident X-ray beam.

Origin of the absent reflections for BCC

o o o o

Affected and unaffected reflections

Now the (200) set of planes incorporates the corner and I atoms simultaneously It is not affected by such phase-cancellation, so the (200) reflection is observed normally. In fact, it turns out that the conditions for absences are satisfied whenever the h index is odd, but not when h is even The complete set of odd-index {n 0 0} symmetry-equivalent reflections does not appear in the diffraction pattern of any I lattice

o o o o

{100} family of lattice planes does not contain the atoms in the body-centre But choice of which iron atoms are the corner, and which the centre, atom is entirely arbitrary {100} planes are exactly in-phase, i.e. 360 extra phase angle for each subsequent plane in the lattice However, the {100}' set occurs at exactly d, but with the same . This causes a beam along the same path as the diffracted {100} beam that is 180 out of phase with the first beam, as shown here:

Lattice type P i iti P Primitive, Body centred, I Face centred, F Side centred, e.g. C Rhombohedral, R

Rule for reflection to be absent N None hkl; h + k + l = 2n +1 hkl; h, k, l not all odd or not all even hkl; h + k = 2n + 1 hkl; h + k + l = 3n + 1, or (h k +l = 3n + 1)

Resulting in total destructive interference and consequently a systematically absent reflection.

Absences due to translational symmetry

o
Symmetry element Affected reflection Rule for reflection to be absent 21, 42 or 63 screw axis along a h00 h = 2n +1 21, 42 or 63 screw axis along b 0k0 k = 2n +1 21, 42 or 63 screw axis along c 00l l = 2n +1 31, 32, 62, 64 screw axis along c* 00l l = 3n +1, +1 3n +2 (not evenly divisible by 3) 41, 43 screw axis along a h00 h = 4n +1, 2 or 3 41, 43 screw axis along b 0k0 k = 4n +1, 2 or 3 41, 43 screw axis along c 00l l = 4n +1, 2 or 3 61, 65 screw axis along c* 00l l = 6n +1, 2, 3, 4, or 5 Glide plane perpendicular to a Translation b/2 (b glide) 0kl k = 2n +1 Translation c/2 (c glide) l = 2n +1 Trans. b/2 + c/2 (n glide) k + l = 2n +1 Trans. b4 + c/4 (d glide) k + l = 4n +1, 2 or 3 Glide plane perpendicular to b Translation a/2 (a g glide) ) h0l h = 2n +1 Translation c/2 (c glide) l = 2n +1 Trans. a/2 + c/2 (n glide) h + l = 2n +1 Trans. a/4 + c/4 (d glide) h + l = 4n +1, 2 or 3 Glide plane perpendicular to c Translation a/2 (a glide) hk0 h = 2n +1 Translation b/2 (b glide) k = 2n +1 Trans. a/2 + b/2 (n glide) h + k = 2n +1 Trans. a/4 + b/4 (d glide) h + k = 4n +1, 2 or 3 * Cells with 3 or 6 fold axes are hexagonal or trigonal, where c is the only direction such axes can have

Exercise
Consider the powder pattern for germanium shown below. Confirm from the systematic absences among the indexed reflections that the space group of elemental germanium is Fd3m. Are there any discrepancies from the expected absences? Why or why not? For Germanium (Fd3m); a = 5.658, and copper radiation with = 1.54056 was employed in y( (%) ) 111 1,1,1 the measurement. measurement Intensity
100 90 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100 110 4,2,2 3,3,1 (83.66,17.4) 5,1,1 5,3,1 6,2,0 4,0,0 3,3,3 (72.80,13.7) (107.30,10.1) (118.86,9.6) (65.99,9.7) (90.05,9.4) 4,4,0 (100.73,5.5) 2 () 120 2,2,0 (45.30,69.2) (27.28,100.0)

311 3,1,1 (53.68,39.7)

The International Tables list the conditions for reflections to be present rather than to be absent. This sort of makes sense because we use the Tables only after we find out what the space group is and we can check the presences.

These are the general conditions for reflections to be present for any crystal in thi space group. This this Thi list li t iincludes l d within ithi it th the conditions diti f for an F F-lattice l tti

These extra conditions for reflections to be present when there are atoms included in the special locations. These apply only to atoms which are located in the special Wyckoff positions.

Thus if only y some of the atoms are on a special Wyckoff positions the extra conditions apply only to the contribution of those atoms to the total scattering. If all atoms in the lattice are at such positions, then these conditions apply completely.