FACULTY OF SCIENCE AND TECHNOLOGY

Exam papers : FYS620 X-ray physi s .

Date : Thursday 25th August 2016 .

Duration : 4 hours (09:00 - 13:00) .

Supporting Material : Approved al ulator .

The set ontains 3 problems distributed on 9 pages (in luding gures).

On page 10 some expressions, physi al onstants and mathemati al identities
whi h may prove useful, are provided.
Extra ts from International Tables for Crystallography volume A (ITA) are
in luded:
• Derivations of symbols and oordinate triplets (ITA pp. 812-815).
Problem 1

The solid phase of mer ury (Hg) belongs to the hexagonal rystal system.
The latti e parameters are a = 3.460 Å and c = 6.702 Å.
There are three atoms in the unit ell with oordinates: (0,0,0), ( 31 , 23 , 23 )
and ( 32 , 13 , 13 ), respe tively.

The following information is available for mer ury:

Element Atomi number Molar mass
Hg 80 200.59 g/mol
Table 1: Element data for mer ury.

a) Determine the volume of the unit ell, Vc , and the density, ρ, for rys-
talline mer ury.

Uranium is known to have an orthorhombi rystal latti e with four atoms

in the unit ell. The oordinates are
1 3 1 1 1 1 1 3
(1) 0, y, (2) 0, ȳ, (3) , + y, (4) , − y,
4 4 2 2 4 2 2 4
where y expresses an arbitrary lo ation.

b) Dedu e the Bravais latti e of uranium and derive an expression for the
stru ture fa tor Fhkl .

Fluorite (CaF2 ) rystallizes in an all-fa e entred ubi latti e, i.e. uorite

has the Bravais latti e cF . The latti e parameter is a = 5.463 Å and the
density is ρ = 3.181 g/ m3 .

Further information related to the elements Ca and F is ompiled in table 2.

The values for µm is asso iated with MoK ᾱ-radiation. MoK ᾱ-radiation has
a wavelength of 0.711 Å.

1
 Element Ca F
Atomi number Z20 9
Molar mass M [g/mol℄ 40.08 19.00
Ionization energies WK [keV℄ 4.034 -
WL2 ,L3 [keV℄ 0.343 -
Mass attenuation oe ient µm = (µ/ρ) [ m2 g−1 ] 19.3 1.63
Table 2: Data for al ium (Ca) and uorine (F). Splitting of energy levels is
not taken into a ount.

For the a tual CaF2 -sample the family of (111) latti e planes is parallel
with the rystal surfa e leading to a (111) s attering geometry denoted as
symmetri al ree tion, f. gure 1 below.
kh

ko

Figure 1: Symmetri al Bragg s attering.

The absorption fa tor, A, is then expressed by1 :
sin θ   µt
A= 1 − e−2µt/ sin θ ≈ 1 −
2µt sin θ
) Determine the linear absorption oe ient, µ, asso iated with MoK ᾱ-
radiation in rystalline CaF2 .
What is the a tual rystal thi kness, t, if absorption leads to an inten-
sity redu tion of 8.0 % for the 111-ree tion ?
MoK ᾱ-radiation ionizes K -ele trons in al ium (Ca) and uorine (F).
d) Cal ulate the wavelength asso iated with se ondary CaKα-radiation
based on the data given in table 2.
Assuming a s reening onstant σ = 1.20, use Moseley's law to deter-
mine the energy (expressed in keV) asso iated with the K -absorption
edge of uorine.

1
The approximation is valid whenever A ≥ 0.9 . θ is the a tual Bragg angle.

2
Problem 2

The following spa e group symbols are given:

Case No. Symbol
a 93 P 42 2 2
b 159 P 3 1 c
Table 3: International symbols for two dierent spa e groups.
From International Tables for Crystallography vol. A.

Spa e-group diagrams showing the relative lo ations and orientations of the
symmetry elements are provided in gure 2 (page 6).

a) Explain the meaning of the symbols that are in luded in the

designation of these two spa e groups.
Compile two lists where you state, based on the appearan e of
graphi al symbols, all symmetry elements present in ea h spa e group.
Point out the underlying point-group symmetry in the two ases.
Classify the spa e groups a ording to their rystal systems.

Figure 3 (page 7) shows the relative lo ations and orientations of the

symmetry elements in ve dierent primitive spa e groups belonging to the
orthorhombi rystal system: 3(a)-(d) omprising P mn21 , P ca21 , P nc2 and
P ba2.

b) Whi h spa e group symbol, P mn21 , P ca21 , P nc2 or P ba2, should be

asso iated with ea h of the four gures 3(a)-(d)?
Whi h spa e group symbol should be assigned to the illustration in
3(e) ?
Determine for ase 3(e) the oordinate-triplets of the symmetry equiv-
alent points of the general position.

3
The sequen e of oordinate triplets of symmetry equivalent points in general
positions asso iated with one of the spa e groups in gure 3 is :

(1) x, y, z (2) x̄, ȳ, z (3) x + 12 , ȳ + 12 , z (4) x̄ + 21 , y + 12 , z

) Constru t the multipli ation table for this spa e group.

Use the pro edure by Fis her and Ko h, International Tables for Crys-
tallography (2006). Volume A, Chapter 11.2, to dedu e the symmetry
operation leading to the oordinate triplet (4) in the above
list of oordinates.
Assign the orre t spa e group asso iated with the given sequen e of
oordinate triplets.

Problem 3

The mineral ooperite, PtS, rystallizes in the tetragonal spa e group P 42 /mmc.
The latti e parameters are er a = 3.470 Å og c = 6.110 Å. There are two
formula units in the unit ell.

The atoms are lo ated at spe ial positions:

Pt: (0, 12 , 0) ( 12 , 0, 21 )

S: ( 12 , 12 , 14 ) ( 12 , 21 , 34 )

Figure 4 shows the atomi form fa tors, f 0 , f ′ and f ′′ for platinum (Pt),
while gure 5 gives the orresponding information for sulfur (S).

The rystalline stru ture is being examined using X-rays of wavelength

λ = 1.200 Å.

a) In a tetragonal unit ell, draw the planes having the Miller indi es
(110) and (101̄).
Determine the interplanar spa ings d110 and d101̄ in ooperite.
Determine the angle between the unit normal ve tors to these planes:
n̂110 and n̂101̄ .

4
 b) Apply Ewald's onstru tion to graphi ally determine h = hmax , the
highest observable order asso iated with (h0h̄) ree tions.
Apply Bragg's law to analyti ally determine the value of hmax
asso iated with (hh0) ree tions.
h is a positive integer.

The stru ture fa tor for PtS an generally be expressed by:

 
n
k h+l
o
h+k+l πl
Fhkl = fPt (−1) + (−1) + 2 (−1) fS cos
2

) State the ree tion ondition leading to Fhkl ≡ 0 .

Determine a tual values for the moduli |F110 | and |F101̄ | and the phase
angles φ110 and φ101̄ .

5
 (a)

(b)

Figure 2: Lo ation of symmetry elements in the spa e groups (a) P 42 2 2

and (b) P 3 1 c.

6
 (a) (b)

( ) (d)

(e)

Figure 3: Lo ation of symmetry elements in ve orthorhombi spa e groups.

7
Figure 4: Atomi s attering fa tor f 0 as fun tion of s = sin θ/λ [Å−1 ] and
the resonan e (dispersion) fa tors f ′ and f ′′ as fun tion of λ for platinum.

8
Figure 5: Atomi s attering fa tor f 0 as fun tion of s = sin θ/λ [Å−1 ] and
the resonan e (dispersion) fa tors f ′ and f ′′ as fun tion of λ for sulfur.

9
Expressions and onstants:

Atomi s attering fa tor:

XZ
fn0 = ρn (r) exp(2πi K · r) dV
j

Debye-Waller fa tor:

Tn (K) = exp −2π 2 K 2 hu2n i

Stru ture fa tor :

X
Fhkl = fn exp(2πi[hxn + kyn + lzn ])
n

Physi al onstants :

Elementary harge e = 1.602 × 10−19 C

Ele tron mass m = 9.109 × 10−31 kg
Plan k onstant h = 6.626 × 10−34 Js
h̄ = 1.055 × 10−34 Js
Boltzmann onstant kB = 1.381 × 10−23 J/K
Avogadro onstant NA = 6.022 × 1023 mol−1
Speed of light c = 2.998 × 108 m/s
Classi al ele tron radius re = 2.818 × 10−15 m

Mathemati al identities :
exp(±iθ) = cos θ ± i sin θ
cos(θ ± φ) = cos θ cos φ ∓ sin θ sin φ
sin(θ ± φ) = sin θ cos φ ± cos θ sin φ
cos 2θ = cos2 θ− sin2 θ   
A+B A−B
cos A + cos B = 2 cos · cos
2 2
   
A+B A − B
sin A + sin B = 2 sin · cos
2 2

10
International Tables for Crystallography (2006). Vol. A, Chapter 11.2, pp. 812–816.
11.2. Derivation of symbols and coordinate triplets
BY W. FISCHER AND E. KOCH
WITH TABLES 11.2.2.1 AND 11.2.2.2 BY H. ARNOLD

11.2.1. Derivation of symbols for symmetry operations related by the symmetry operation or by the algebraic procedure
from coordinate triplets or matrix pairs described below.
In the space-group tables, all symmetry operations with 0  w < 1
are listed explicitly. As a consequence, the number of entries under
the heading Symmetry operations equals the multiplicity of the Example
0 1 0 1
general position. For space groups with centred unit cells, w  1 0 0 1 0
may result if the centring translations are applied to the explicitly B C B1C
listed coordinate triplets. In those cases, all w values have been z, y ‡ 12, x ‡ 12 ) W ˆ @ 0 1 0 A, wˆ@2A
reduced modulo 1 for the derivation of the corresponding symmetry 1 0 0 1
2
operations (see Section 2.2.9). In addition to the tabulated symmetry
) tr…W † ˆ 1, det …W† ˆ 1
operations, each space group contains an infinite number of further
operations obtained by application of integral lattice translations. In ) fourfold rotoinversion;
many cases, it is not trivial to obtain the additional symmetry 0 10 1 0 1 0 1
0 0 1 x 0 x
operations (cf. Part 4) from the ones listed. Therefore, a general B CB C B 1 C B C
procedure is described below by which symbols for symmetry 
…W, w†x ˆ x ) @ 0 1 0 A@ y A ‡ @ 2 A ˆ @ y A
operations as described in Section 11.1.2 may be derived from 1 0 0 z 1
z
2
coordinate triplets or, more specifically, from the corresponding
matrix pairs (W, w). [For a similar treatment of this topic, see ) x ˆ y ˆ z ˆ 14
Wondratschek & Neubüser (1967).] This procedure may also be ) inversion point at 4 4 4;
111
applied to cases where space groups are given in descriptions not
contained in International Tables. In practice, two cases may be …W 2 , W w ‡ w†x ˆ x
0 10 1 0 1 1 0 1
distinguished: 1 0 0 x x
2
(i) The matrix W is the unit matrix: B CB C B C B C
) @ 0 1 0 A@ y A ‡ @ 0 A ˆ @ y A
0 1
1 0 0 0 0 1 z 1
z
W ˆ I ˆ @ 0 1 0 A:
2
) x ˆ z ˆ 14, y undetermined
0 0 1
) rotoinversion axis at 14 y 14;
011 0 10 1 1 0 1 0 1
In this case, the symmetry operation is a translation with translation 0 0 1 0 z
4 4
vector w. B1C B 1 0 A@ 1 A ‡ @ A ˆ @ 1 C
C B C B C B
…W , w†@ 4 A ˆ @ 0 4
1
2 4A
Example 0 1 011 z 1 0 0 z 1
2
1
4
1 0 0
B C B C
2 ) the rotation sense is negative as verified by
x‡ 1
2, y ‡ 1
2, z ) W ˆ @ 0 1 0 A ˆ I, w ˆ @ 12 A
geometrical inspection.
0 0 1 0
) 4 1, y, 1; 1, 1, 1:
4 4 4 4 4
) translation with translation vector w ˆ 12 a ‡ 12b
…C centring†: (b) W corresponds to an n-fold rotation. (W, w) is thus either a
rotation or a screw rotation. To distinguish between these
(ii) The matrix W is not the unit matrix: W 6ˆ I: In this case, one alternatives, …W , w†n ˆ …I, t† has to be calculated. For t ˆ o,
calculates the trace, tr…W† ˆ W11 ‡ W22 ‡ W33 , and the determi- …W , w† describes a pure rotation, the rotation axis of which is
nant, det …W †, and identifies the type of the rotation part of the found by solving …W , w†x ˆ x. For t 6ˆ o, (W, w) describes a screw
symmetry operation from Table 11.2.1.1. rotation with screw part wg ˆ …1=n†t. The location of the screw axis
One has to distinguish three subcases: is found as the set of fixed points for the corresponding pure rotation
(a) W corresponds to a rotoinversion. The inversion point X is …W, wl † with wl ˆ w wg , i.e. by solving …W, wl †x ˆ x. The sense
obtained by solving the equation …W , w†x ˆ x. For a rotoinver- of the rotation may be found either by geometrical inspection or by
sion other than 1, the location of the axis follows from the the algebraic procedure described below.
equation …W, w†2 x ˆ …W 2 , Ww ‡ w†x ˆ x. The rotation sense
may be found either by geometrical inspection of a pair of points
Example 0 1 0 1
0 0 1 0
B C B1C
Table 11.2.1.1. Identification of the type of the rotation part of z, x ‡ 12, y ) W ˆ @ 1 0 0 A, wˆ@2A
the symmetry operation 0
0 1 0
tr…W † 3 2 1 0 1 2 3
) tr…W † ˆ 0, det …W † ˆ 1
det …W † ) threefold rotation or screw rotation;
1 2 3 4 6 1 …W , w†3 ˆ …W 3 , W 2 w ‡ Ww ‡ w†
1 
1 
6 
4 
3 m and
812

Copyright © 2006 International Union of Crystallography

 11.2. DERIVATION OF SYMBOLS AND COORDINATE TRIPLETS
1 0
1
2
For rotations or screw rotations, the sense is positive for d > 0 and
B 1C negative for d < 0. For rotoinversions, the sense is positive for
W w ‡ Ww ‡ w ˆ t ˆ @ 2 A
2
d < 0 and negative for d > 0.
1
2
) threefold screw rotation with screw part Example
0 11 According to example in (b) above, the triplet 0z, x1‡ 12, y
1
6 6
B 1C B 1C
wg ˆ 13 t ˆ @ 6 A; represents a threefold screw rotation with screw part @ 6 A and
1 1
6 6
…W, wl †x ˆ x screw axis at x, 13 x, 16 x. To obtain the sense of the rotation,
0 10 1 0 1 0 1 the points 013 16 and 16 160 are used as P0 and P1 on the axis and the
0 0 1 x 1
6 x points 000 and 0120 as P2 and P3 outside the axis. The resulting
B CB C B 1C B C
) @ 1 0 0 A@ y A ‡ @ 3A ˆ @yA vectors are
0 11 0 1 0 1
0 1 0 z 1
z 6
0 0
6
B C B C B C
)yˆ 1
x; zˆ 1
x; x undetermined v1 ˆ @ 16 A, v2 ˆ @ 13 A, v3 ˆ @ 16 A
3 6
1 1 1
) screw axis at x, 13
x x, 16
 6
 6 6
 1
0 0 
(for the sense of rotation see example below):  6
 1 1
)dˆ 1 1
6  ˆ 72 > 0
 6 3
(c) W corresponds to a (glide) reflection. The glide char-  1 1 1
6 6 6
acter is now found by means of the equation
) the sense of the rotation is positive
…W, w†2 ˆ …I, Ww ‡ w† ˆ …I, t†. For t ˆ o, (W, w) describes a
pure reflection and the location of the mirror plane follows from ) 3‡ … 6, 6, 6†
1 1 1
x, 13 x, 16 x:
…W, w†x ˆ x. For t 6ˆ o, (W, w) corresponds to a glide reflection
with glide part wg ˆ 12 t. The location of the glide plane is the set of
fixed points for the corresponding pure reflection …W , wl † ˆ
…W, w 12 t† and is thus calculated by solving …W, wl †x ˆ x. 11.2.2. Derivation of coordinate triplets from symbols for
symmetry operations
Example A particular symmetry operation is uniquely described by its
1 0 011
0 1 0 2
symbol, as introduced in Section 11.1.2, and the coordinate system
B C B C to which it refers. In the examples of the previous section, the
y ‡ 12, x, z ‡ 34 ) W ˆ @ 1 0 0 A, w ˆ @0A symbols have been derived from the coordinate triplets representing
3
0 0 1 4 the respective symmetry operations. Inversely, the pair (W, w) of
the symmetry operation and the coordinate triplet of the image point
) tr…W† ˆ 1, det …W† ˆ 1
can be deduced from the symbol.
) reflection or glide reflection; (i) For all symmetry operations of space groups, the rotation
0 1
1 parts W referring to conventional coordinate systems are listed in
2 Tables 11.2.2.1 and 11.2.2.2 as matrices for point-group symmetry
B 1C
…W , w†2 ˆ …W 2 , W w ‡ w†, Ww ‡ w ˆ t ˆ @ 2A operations. For rotoinversions, the position of the inversion point at
3 0, 0, 0 is not explicitly given.
2
(ii) The location part wl of w may easily be derived from
) glide reflection with glide part 0 1 0 1 0 1
0 11 x0 x0 x0
4 …W, wl † y0 ˆ y0 , i:e: wl ˆ …I W † y0 A
@ A @ A @
B 1C
wg ˆ 12 t ˆ @ 4 A; z0 z0 z0
3
4
10 1 0 1 1 0 1
0 with x0 , y0 , z0 being the coordinate triplet of the inversion point of a
0 1 0 x 4
x rotoinversion or the coordinate triplet of an arbitrary fixed point of
B CB C B 1 C B C any other symmetry operation. The intrinsic translation part wg of
…W , wl †x ˆ x ) @ 1 0 0 A@ y A ‡ @ 4 A ˆ @ y A w is given explicitly in the symbol of the symmetry operation, so
0 0 1 z 0 z that the translation part w is obtained as
0 1
) y ˆ x ‡ 14; x, z undetermined w1
) glide plane d at x, x ‡ 14, z w ˆ wg ‡ wl ˆ w2 A:
@
w3
) d…14, 4, 4†
1 3
x, x ‡ 14, z:
(iii) The coordinate triplet ~x, ~y, ~z corresponding to the symmetry
The sense of a pure or screw rotation or of a rotoinversion may be operation is now given by
calculated as follows: One takes two arbitrary points P0 and P1 on
the rotation axis, P0 having the lower value for the free parameter of ~x ˆ W 11 x ‡ W 12 y ‡ W 13 z ‡ w1
the axis. One takes a point P2 not lying on the axis and generates P3 ~y ˆ W 21 x ‡ W 22 y ‡ W 23 z ‡ w2
from P2 by the symmetry operation under consideration. One
calculates the determinant d of the matrix …v1 , v2 , v3 † composed of ~z ˆ W 31 x ‡ W 32 y ‡ W 33 z ‡ w3 :
ƒƒ! ƒƒ! ƒƒ!
the components of vectors v1 ˆ P0 P1 , v2 ˆ P0 P2 and v3 ˆ P0 P3 .
813
 11. SYMMETRY OPERATIONS
Example w ˆ wg ‡ wl
4 …0, 0, 34† 14, 1 0 1 011 011
4, z
tetragonal system 0
0 1 2 2
0 1 0 B0C B C B C
) w ˆ @ A ‡ @0A ˆ @0A
4 0, 0, z ) W ˆ @ 1 0 0 A from Table 11.2.2.1: 3 3
0 0 1 4 0 4
) ~x ˆ y ‡ 12, ~y ˆ x, ~z ˆ z ‡ 34:
x0 ˆ 14, y0 ˆ 14, z0 ˆ 0 is a fixed point of 4 14, 14, z, i.e. a point on
the screw axis.
0 1
x0
B C
wl ˆ …I W †@ y0 A
z0 References
0 10 1 1 0 1 1
1 1 0 4 2 Wondratschek, H. & Neubüser, J. (1967). Determination of the
B CB C B C symmetry elements of a space group from the ‘general positions’
) wl ˆ @ 1 1 0 A@ 14 A ˆ @ 0 A;
listed in International Tables for X-ray Crystallography, Vol. I.
0 0 0 0 0 Acta Cryst. 23, 349–352.

814