international school on fundamental …cloud.crm2.uhp-nancy.fr/pdf/uberlandia/aroyo_point.pdf ·...
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INTERNATIONAL SCHOOL ON FUNDAMENTAL CRYSTALLOGRAPHY
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CRYSTALLOGRAPHIC POINT GROUPS
Bilbao Crystallographic Server
http://www.cryst.ehu.es
Cesar Capillas, UPV/EHU 1
Mois I. AroyoUniversidad del Pais Vasco, Bilbao, Spain
(short review)
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The equilateral triangle allows six symmetry operations: rotations by 120 and 240 around its centre, reflections through the three thick lines intersecting the centre, and the identity operation.
1. Crystallographic symmetry operations
Symmetry operations of an object
The isometries which map the object onto itself are called symmetry operations of this object. The symmetry of the object is the set of all its symmetry operations.
If the object is a crystal pattern, representing a real crystal, its symmetry operations are called crystallographic symmetry operations.
Crystallographic symmetry operations
The symmetry operations are isometries, i.e. they are special kind of mappings between an object and its image that leave all distances and angles invariant.
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GROUP THEORY(few basic facts)
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Crystallographic symmetry operations in the plane
my
Mirror line my at 0,y
x
y=
-x
y =-1
1
x
y
det -1
1= ? tr -1
1= ?
Matrix representation
Fixed points
myxf
yf=
xf
yf
Mirror symmetry operation
drawing: M.M. JulianFoundations of Crystallography
Taylor & Francis, 2008c�
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2-fold rotation
2zx
y=
-x
-x =-1
-1
x
y
det -1
-1=
tr -1
-1= ?
Symmetry operations in the planeMatrix representations
3+ x
y=
-y
x-y =0 -1
1 -1
x
y
det =
tr = ?
Matrix representation
0 -1
1 -1
0 -1
1 -1
??
3-fold rotation
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GROUP AXIOMS
1. CLOSURE
2. IDENTITY
3. INVERSE ELEMENT
4. ASSOCIATIVITY
g1o g2=g12 g1, g2, g12∈G
g o e = e o g = g
g o g-1= e
(g1o g2)o g3= g1o ( g2 o g3)= g1o g2 o g3
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Group properties and presentation
1. Order of a group
2. Multiplication table
3. Group generators
a set of elements such that each element of the group can be obtained as a product of the generators
number of elements
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Group Properties
Multiplication table
Group generators a set of elements such that each element of the group can be obtained as a product of the generators
4. How to define a group
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G G’
.. ..
G={g} G’={g’}Φ(g)=g’
Φ-1: G’ G
Φ(g1)Φ(g2)= Φ(g1g2)homomorphic condition
Isomorphic groups
Φ-1(g’)=g
Φ: G G’
-groups with the same multiplication table
g1g2
.g1g2
Φ(g1)
Φ(g2)
Φ(g1g2).
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Crystallographic Point Groups in 2D
Point group 2 = {1,2}-group axioms?
-order of 2?
-multiplication table
-1
-1
-1
-1
1
1=x2 x 2 =
Where is the two-fold point?
Motif with symmetry of 2
-generators of 2?
drawing: M.M. JulianFoundations of Crystallography
Taylor & Francis, 2008c�
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Crystallographic Point Groups in 2D
Point group m = {1,m}
-group axioms?
-order of m?
-multiplication table
-1
1
-1
1
1
1=xm x m =
Whereis the mirror line?
Motif with symmetry of m
-generators of m?drawing: M.M. Julian
Foundations of CrystallographyTaylor & Francis, 2008c�
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GG’.. ..
Φ(g1)Φ(g2)= Φ(g1 g2)
Isomorphic groups
-groups with the same multiplication table
Point group 2 = {1,2}
Φ(g)=g’
Φ-1(g’)=g
Point group m = {1,m}
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Crystallographic Point Groups in 2D
Point group 1 = {1}
-group axioms?
-order of 1?
-multiplication table
1
1
1
1
1
1=x1 x 1 =
Motif with symmetry of 1
-generators of 1?
drawing: M.M. JulianFoundations of Crystallography
Taylor & Francis, 2008c�
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Problem 2.1
Consider the model of the molecule of the organic semiconductor pentacene (C22H14):
-symmetry operations: matrix and (x,y) presentation
-multiplication table-generators
Determine:
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Problem 2.2
Consider the symmetry group of the square. Determine:
-symmetry operations: matrix and (x,y) presentation
-multiplication table
-generators
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Visualization of Crystallographic Point Groups
- general position diagram - symmetry elements diagram
Stereographic Projections
Points P in the projection plane
P’’
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EXAMPLE
general position symmetry elements
Stereographic Projections of mm2
Molecule of pentacene
Point group mm2 = {1,2z,mx,my}
Stereographic projections diagrams
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Problem 2.2 (cont.)
general position symmetry elements
Stereographic Projections of 4mm
diagram diagram
? ?
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Problem 2.3 (additional)
Consider the symmetry group of the equilateral triangle. Determine:
-symmetry operations: matrix and (x,y) presentation
-multiplication table
-generators
-general-position and symmetry-elements stereographic projection diagrams;
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Conjugate elements
Conjugate elements gi ~ gk if ∃ g: g-1gig = gk,where g, gi, gk, ∈ G
Classes of conjugate elements
L(gi)={gj| g-1gig = gj, g∈G}
Conjugation-properties
(iii)
(i) L(gi) ∩ L(gj) = {∅}, if gi ∉ L(gj)
(ii) |L(gi)| is a divisor of |G|
(iv) if gi, gj ∈ L, then (gi)k=(gj)k= e
L(e)={e}
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Example (Problem 2.2):
The group of the square 4mm
Classes of conjugate elements: {1}, {2},{4,4-},{mx,my}, {m+,m-}
Classes of conjugate elements
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Problem 2.1 (cont)EXERCISES
Distribute the symmetry elements of the group mm2 = {1,2z,mx,my} in classes of conjugate elements.
multiplication table
stereographic projection
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CRYSTALLOGRAPHIC POINT GROUPS(brief overview)
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Symmetry operations in 3DRotations
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Rotation Crystallographic Point Groups in 3D
Cyclic: 1(C1), 2(C2), 3(C3), 4(C4), 6(C6)
Dihedral: 222(D2), 32(D3), 422(D4), 622(D6)
Cubic: 23 (T), 432 (O)
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Dihedral Point Groups
{e,2z, 2y,2x}
{e,3z,3z ,21,22,23}
{e,4z,4z, 2z,2y,2x,2+,2-}
{e,6z,6z, 3z,3z, 2z
21,22,23, 21,22,23}
222
32
422
622
´ ´ ´
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Cubic Rotational Point Groups
23 (T)
{e, 2x, 2y, 2z, 31,31,32,32,33,33,34,34}
{e, 2x, 2y, 2z,4x,4x,4y,4y,4z,4z
31,31,32,32,33,33,34,34
21,22,23,24,25,26}
432(O)
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Symmetry operations in 3DRotoinvertions
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Symmetry operations in 3DRotoinvertions
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Symmetry operations in 3DRotoinversions
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Symmetry operations in 3D3 Roto-inversion
generalview
down the symmetry axis
3+generalview
3+down thesymmetry axis
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Crystallographic Point Groups in 3D
Proper rotations: det =+1: 1, 2, 3, 4, 6
Improper rotations: det =-1:-2
-3
-4
-6
-1
Hermann-Mauguin symbolism (International Tables A)
-symmetry elements in decreasing order of symmetry (except for two cubic groups: 23 and m ) -
3
-symmetry elements along primary, secondary and ternary symmetry directions
rotations: by the axes of rotationplanes: by the normals to the planes
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Crystal systems and Crystallographic point groups
primary secondary ternary
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Crystal systems and Crystallographic point groups
primary secondary ternary
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Crystallographic Point Groups in 3D
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The group G= is called a direct-product group
Direct-product groups
G1 x G2 {(g1,e2), g1∈G1} ≅ G1
Let G1 and G2 are two groups. The set of all pairs {(g1,g2), g1∈G1, g2∈G2} forms a group with respect to the product: (g1,g2) (g’1,g’2)= (g1g’1, g2g’2).
G1 x G2
Properties of
G1 x G2
G1 x G2
G1 x G2 {(e1,g2), g2∈G2} ≅ G2
{(e1,g2), g2∈G1}= {(e1,e2)}{(g1,e2), g1∈G1} ∩
∀ (g1,g2)∈ G1 x G2 : (g1,g2)= (g1,e2) (e1,g2)
(i)
(ii)
(iii)
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G1 x {1,1}=G1+1.G1
Examples: Direct product groups
G2={1,1} group of inversion
Point group mm2 = {1,2z,mx,my}G1={1,2z} G2={1,mx}G1 x G2= {1.1, 2z.1, 1.mx, 2zmx=my}
Centro-symmetrical groupsG1: rotational groups
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Crystallographic point groups and abstract groups
Cyclic groupsAbelian non-cyclic groups
Non-Abelian groups
Direct products of non-Abelian groups with cyclic groups of order 2
Crystal classes
Affine equivalence Abstract
groups
32 18
Abstractgroups
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Crystallographic point groups
as abstract groups
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Crystallographic Point Groups
G G+1G G(G’) G’+1(G-G’)
1 (C1) 1+1.1=1 (Ci) ---- -----
2 (C2) 2+1.2=2/m (C2h) 2(1) m (Cs)
3 (C3) 3+1.3=3 (C3i or S6) ---- ----
4 (C4) 4+1.4=4/m (C4h) 4(2) 4 (S4)
6 (C6) 6+1.6=6/m (C6h) 6(3) 6 (C3h)
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Crystallographic Point Groups
G G+1G G(G’) G’+1(G-G’)
222 (D2) 222+1.222=2/m2/m2/m 222(2) 2mm (C2v)
4/mmm(D4h) 422(222) 42m (D2d)
32 (D3) 32+1.32=32/m 3m(D3d) 32(3) 3m (C3v)
422 (D4) 422+1.422=4/m2/m2/m 422(4) 4mm (C4v)
6/mmm(D6h) 622(32) 62m (D3h) 622 (D6) 622+1.622=6/m2/m2/m 622(6) 6mm (C6v)
23 (T) 23+1.23=2/m3 m3 (Th) ---- -----
mmm (D2h)
432 (O) 432+1.432=4/m32/m 432(23) 43m (Td) m3m(Oh)
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Crystallographic Point Groups
422 e 4z 4z 2z 2x 2y 2+2-
4mm e 4z 4z 2z mx my m+m-
42m e 4z 4z 2z 2x 2y m+m-
4m2 e 4z 4z 2z mx my 2+2-
Groups isomorphic to 422
Groups isomorphic to 622
622 e 6z6z 3z3z 2z 212223 212223´´ ´
6mm e 6z6z 3z3z 2z m1m2m3 m1m2m3´ ´ ´62m e 6z6z 3z3z mz 212223 m1m2m3´ ´ ´6m2 e 6z6z 3z3z mz m1m2m3 212223´ ´ ´
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Problem 2.4
Consider the following three pairs of stereographic projections. Each of them correspond to a crystallographic point group isomorphic to 4mm:
(i) Determine those point groups by indicating their symbols, symmetry operations and possible sets of generators;(ii) Construct the corresponding multiplication tables;(iii) For each of the isomorphic point groups indicate the one-to-one correspondence with the symmetry operations of 4mm.
4mm
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Crystallographic Point Groups in 3D
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?xy
z
AB4 type molecule
Determine the symmetry group of the configuration:
Example Symmetry groups of molecules
Hint: cubic crystal systemsymmetry directions: [100] [111][110]
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Problem 2.5(a)
Determine the symmetry elements and the corresponding point groups for each of the following models of molecules:
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Problem 2.5(b)
Determine the symmetry elements and the corresponding point groups for each of the following models of molecules:
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I. Subgroups: index, coset decomposition and normal subgroups
II. Conjugate subgroups
III. Group-subgroup graphs
GROUP-SUBGROUP RELATIONS
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Subgroups: Some basic results (summary)
Subgroup H < G
1. H={e,h1,h2,...,hk} ⊂ G2. H satisfies the group axioms of G
Proper subgroups H < G, and trivial subgroup: {e}, G
Index of the subgroup H in G: [i]=|G|/|H| (order of G)/(order of H)
Maximal subgroup H of GNO subgroup Z exists such that:
H < Z < G
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EXERCISES
Problem 2.6 Consider the group of the square and determine its subgroups
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Multiplication table of 3m
mx
my
mxxx
y
Problem 2.7 (additional)
(ii) Distribute the subgroups into classes of conjugate subgroups;
(i) Consider the group of the equilateral triangle and determine its subgroups;
(iii) Construct the maximal subgroup graph of 3m
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Coset decomposition G:H
Group-subgroup pair H < G
left coset decomposition
right coset decomposition
G=H+g2H+...+gmH, gi∉H, m=index of H in G
G=H+Hg2+...+Hgm, gi∉Hm=index of H in G
Coset decomposition-properties
(i) giH ∩ gjH = {∅}, if gi ∉ gjH
(ii) |giH| = |H|
(iii) giH = gjH, gi ∈ gjH
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Theorem of Lagrange
group G of order |G|subgroup H<G of order |H|
then|H| is a divisor of |G|and [i]=|G:H|
Corollary The order k of any element of G,gk=e, is a divisor of |G|
Normal subgroups
Hgj= gjH, for all gj=1, ..., [i]
Coset decomposition G:H
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EXERCISES
Problem 2.9 Demonstrate that H is always a normal subgroup if |G:H|=2.
Problem 2.8
Consider the subgroup {e,2} of 4mm, of index 4:
-Write down and compare the right and left coset decompositions of 4mm with respect to {e,2};
-Are the right and left coset decompositions of 4mm with respect to {e,2} equal or different? Can you comment why?
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Conjugate subgroups
Conjugate subgroups Let H1<G, H2<G
then, H1 ~ H2, if ∃ g∈G: g-1H1g = H2
(i) Classes of conjugate subgroups: L(H)
(ii) If H1 ~ H2, then H1 ≅ H2
(iii) |L(H)| is a divisor of |G|/|H|
Normal subgroup
H G, if g-1H g = H, for ∀g∈G
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EXERCISES
Problem 2.6 (cont) Distribute the subgroups of the group of the square into classes of conjugate subgroups
Hint: The stereographic projections could be rather helpful
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Complete and contracted group-subgroup graphs
Complete graph of maximal subgroups
Contracted graph of maximal subgroups
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Group-subgroup relations of point groupsInternational Tables for Crystallography, Vol. A, Chapter 10
Hahn and Klapper
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Factor group
product of sets: Kj={gj1,gj2,...,gjn}Kk={gk1,gk2,...,gkm}
Kj Kk={ gjpgkq=gr | gjp ∈ Kj, gkq ∈Kk} Each element gr is taken only once in the product Kj Kk
G={e, g2, ...,gp} {
factor group G/H: H GG=H+g2H+...+gmH, gi∉H, G/H={H, g2H, ..., gmH}
(i) (giH)(gjH) = gijH(ii) (giH)H =H(giH)= giH
(iii) (giH)-1 = (gi-1)H
group axioms:
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Problem 2.8 (cont)
Consider the normal subgroup {e,2} of 4mm, of index 4, and the coset decomposition 4mm: {e,2}:
(3) Show that the cosets of the decomposition 4mm:{e,2} fulfil the group axioms and form a factor group
(4) Multiplication table of the factor group
(5) A crystallographic point group isomorphic to the factor group?
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GENERATION OF CRYSTALLOGRAPHIC POINT
GROUPS
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Generation of point groups
Set of generators of a group is a set of group elements such that each element of the group can be obtained as an ordered product of the generators
g1 - identityg2, g3, ... - generate the rest of elements
Composition series: 1 Z2 Z3 ... Gindex 2 or 3
Crystallographic groups are solvable groups
W=(gh) * (gh-1) * ... * (g2) * g1kh kh-1 k2
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Example Generation of the group of the square
Composition series: 1 2 4 4mmStep 1:
1 ={1}
Step 2: 2 = {1} + 2z {1}
Step 3: 4 ={1,2} + 4z {1,2}
Step 4: 4mm = 4 + mx 4
[2] [2] [2]
2z 4z mx
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Generation of sub-cubic point groups
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Composition series of cubic point groups and their subgroups
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Generation of sub-hexagonal point groups
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Composition series of hexagonal point groups and their subgroups
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Problem 2.10
Generate the symmetry operations of the group 4/mmm following its composition series.
Generate the symmetry operations of the group 3m following its composition series.
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GENERAL AND SPECIAL WYCKOFF POSITIONS
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WXo = Xo
Site-symmetry group So={W} of a point Xo
General and special Wyckoff positions
=
General position Xo S= 1 ={1}
Special position Xo S> 1 ={1,...,}
a b c
d e f
g h i
x0
y0
z0
x0
y0
z0
Site-symmetry groups: oriented symbols
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General and special Wyckoff positions
Point group 2 = {1,2z}
WXo = Xo
Site-symmetry group So={W} of a point Xo=(0,0,z)
=2z: 0
0
z
-1
-1
1
0
0
z
So = 2
2 b 1 (x,y,z) (-x,-y,z)
1 a 2 (0,0,z)
Example
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General and special Wyckoff positions
Point group mm2 = {1,2z,mx,my}
WXo = Xo
Site-symmetry group So={W} of a point Xo=(0,0,0)
=2z:
=my:
0
0
z
-1
-1
1
1
-1
1
0
0
z
0
0
z
0
0
z
So = mm2
2 b .m. (x,0,z) (-x,0,z)
2 c m.. (0,y,z) (0,-y,z)
4 d 1 (x,y,z) (-x,-y,z) (x,-y,z) (-x,y,z)
1 a mm2 (0,0,z)
Example
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Problem 2.11EXERCISES
Consider the symmetry group of the square 4mm and the point group 422 that is isomorphic to it.
Determine the general and special Wyckoff positions of the two groups.
Hint: The stereographic projections could be rather helpful
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EXAMPLE
Group-subgroup pair mm2 >2, [i]=2
mm2
x1,y1,z1 2 b 1
Wyckoff positions splitting schemes
4 d 1 (x,y,z) (-x,-y,z) (x,-y,z) (-x,y,z)
-x1,-y1,z1
x,-y,z=x2,y2,z2 2 b 1 -x,y,z=-x2,-y2,z2
x,y,z=-x,-y,z=
2
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Problem 2.12EXERCISES
Consider the general and special Wyckoff positions of the symmetry group of the square 4mm and those of its subgroup mm2 of index 2.
Determine the splitting schemes of the general and special Wyckoff positions for 4mm > mm2.
Hint: The stereographic projections could be rather helpful
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GROUP-SUPERGROUPRELATIONS
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Supergroups: Some basic results (summary)
Supergroup G>H
H={e,h1,h2,...,hk} ⊂ G
Proper supergroups G>H, and trivial supergroup: H
Index of the group H in supergroup G: [i]=|G|/|H| (order of G)/(order of H)
Minimal supergroups G of H
NO subgroup Z exists such that: H < Z < G
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The Supergroup Problem
Given a group-subgroup pair G>H of index [i]
Determine: all Gk>H of index [i], Gi≃G
H
G G2 G3 Gn...
all Gk>H contain H as subgroup
H
G
[i] [i]
Gk=H+g2H+...+gikH
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Example: Supergroup problem
Group-subgroup pair422>222
222
422
[2]
Supergroups 422 of the group 222
222
How many are the subgroups 222 of 422?
422 ?How many are
the supergroups 422 of 222?
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Example: Supergroup problem
Group-subgroup pair422>222
2z2x2y
422
[2]
Supergroups 422 of the group 222
222
4z22
2z2+2-
4x22 4y22
[2]
4z22=222+4z2224y22=222+4y2224x22=222+4x222
4z22= 2z2x2y +4z(2z2x2y)4z22= 2z2+2- +4z(2z2+2-)
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NORMALIZERS
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Normalizer of H in G
Normal subgroup
H G, if g-1H g = H, for ∀g∈G
Normalizer of H in G, H<G
NG(H) ={g∈G, if g-1H g = H}
G ≥ NG(H) ≥ H
What is the normalizer NG(H) if H G?
Number of subgroups Hi<G in a conjugate class
n=[G:NG(H)]
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Problem 2.13
Consider the group 4mm and its subgroups of index 4. Determine their normalizers in 4mm. Distribute the subgroups into conjugacy classes with the help of their normalizers in 4mm.
Hint: The stereographic projections could be rather helpful
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Problem 2.10 SOLUTION
{1,my}
Normalizer of {1,my} in 4mm
4mm
{1,mx}
{e,2,4,4-1,mx,my,m+,m-}
2mm={e,2,mx,my}
Conjugate subgroups: 4mm=2mm+4(2mm)
{ }
{1,my}