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4/24/2013

L. Viciu| AC II | Symmetry in 2D

1

Outlook

•

•

•

•

•

•

**Symmetry: definitions, unit cell choice
**

Symmetry operations in 2D

Symmetry combinations

Plane Point groups

Plane (space) groups

Finding the plane group: examples

4/24/2013

L. Viciu| AC II | Symmetry in 2D

2

Symmetry

Symmetry is the preservation of form and configuration across a

point, a line, or a plane.

The techniques that are used to "take a shape and match it exactly to

another” are called transformations

Inorganic crystals usually have the shape which reflects their internal

symmetry

4/24/2013

L. Viciu| AC II | Symmetry in 2D

3

Motif/Basis = the repeating unit of a pattern (ex. an atom. a molecule etc. a group of atoms.) Unit cell = The smallest repetitive volume of the crystal. which when stacked together with replication reproduces the whole crystal 4/24/2013 L. Viciu| AC II | Symmetry in 2D 4 .Lattice = an array of points repeating periodically in space (2D or 3D).

Unit cell convention By convention the unit cell is chosen so that it is as small as possible while reflecting the full symmetry of the lattice (b) to (e) correct unit cell: choice of origin is arbitrary but the cells should be identical. Viciu| AC II | Symmetry in 2D 5 A. West: Solid state chemistry and its applications . (f) incorrect unit cell: not permissible to isolate unit cells from each other (1 and 2 are not identical) 4/24/2013 L.

Some Definitions • Symmetry element: An imaginary geometric entity (line. plane) about which a symmetry operation takes place • Symmetry Operation: a permutation of atoms such that an object (molecule or crystal) is transformed into a state indistinguishable from the starting state • Invariant point: point that maps onto itself • Asymmetric unit: The minimum unit from which the structure can be generated by symmetry operations 4/24/2013 L. Viciu| AC II | Symmetry in 2D 6 . point.

From molecular point group to space groups Complete consideration of all symmetry elements and translation yields to the space groups benzene D6h or 6/mmm Point group 4/24/2013 graphene p6mm Plane group = point group symmetry + in plane translation L. Viciu| AC II | Symmetry in 2D graphite P63/mmc Space group = point group symmetry + in 3D translation 7 .

reflections 4. glide reflections • Symmetry operations in 3D: the same as in 2D + inversion center. rotations 3. translation 2.• Symmetry operations in 2D*: 1. Viciu| AC II | Symmetry in 2D 8 . rotoinversions and screw axes * Besides identity 4/24/2013 L.

4/24/2013 L. Translation (“move”) Translation moves all the points in the asymmetric unit the same distance in the same direction. Translation has no effect on the chirality of figures in the plane.1. Viciu| AC II | Symmetry in 2D 9 . There are no invariant points (points that map onto themselves) under a translation.

A rotation does not change the chirality of figures. the center of rotation. Rotations A rotation turns all the points in the asymmetric unit around one axis. The center of rotation is the only invariant point. 4/24/2013 L. Viciu| AC II | Symmetry in 2D 10 .2.

(monad) (diad) Axes perpendicular to the plane Axes parallel to the plane three fold rotation axis four fold rotation axis six fold rotation axis (triad) (Tetrad) (Hexad) MOLECULES CRYSTALS 4/24/2013 L.Symbols for symmetry axes Drawn symbol One fold rotation axis two fold rotation axis --. Viciu| AC II | Symmetry in 2D 11 .

The points along the mirror line are all invariant points A reflection changes the chirality of any figures in the asymmetric unit • • Symbol: m Representation: a solid line 4/24/2013 L.3. Viciu| AC II | Symmetry in 2D 12 . Reflections A reflection flips all points in the asymmetric unit over a line called mirror.

Viciu| AC II | Symmetry in 2D 13 . Glide Reflections Glide reflection reflects the asymmetric unit across a mirror and then translates it parallel to the mirror There are no invariant points under a glide reflection. • • Symbol: g Representation: a dashed line 4/24/2013 L. A glide plane changes the chirality of figures in the asymmetric unit.4.

Viciu| AC II | Symmetry in 2D 14 . based on the symmetries in the pattern 4/24/2013 L.Point group symmetry • Point group = the collection of symmetry elements of an isolated shape • Point group symmetry does not consider translation! • The symmetry operations must leave every point in the lattice identical therefore the lattice symmetry is also described as the lattice point symmetry • Plane symmetry group or plane crystallographic group is a mathematical classification of a two-dimensional repetitive pattern.

Viciu| AC II | Symmetry in 2D 15 .Examples of plane symmetry in architecture 4/24/2013 L.

2 (two fold axis) 3. 4 (four fold axis) 5. Viciu| AC II | Symmetry in 2D 6 mm (6-fold axis and 6 mirror lines)* 16 * Second “m” in the symbol refers to the second type of mirror line . 1 (one fold axis) 2.Crystallographic plane point groups = 10 1. 6 (six fold axis) 4/24/2013 6. 3 (three fold axis) 4. L. 3 m (one 3-fold axis and three mirror lines) 9. 4 mm (4-fold axis and four mirror lines)* 10. 7. m (mirror line) 2 mm (two mirror lines and a 2-fold axis)* 8.

axes are not compatible with translation non-periodic two dimensional patterns Ex: Starfish 5m (five fold axis + mirror) Wikipedia.Non-periodic 2D patterns • 5-fold . etc. 7-fold.org A Penrose tiling Group of atoms or viruses can form “quasicrystals” (quasicristals = ordered structural forms that are non-periodic) Electron diffraction of a Al-Mn quasicrystal showing 5-fold symmetry by Dan Shechtman 4/24/2013 L. Viciu| AC II | Symmetry in 2D 17 .

Viciu| AC II | Symmetry in 2D 18 .http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2011/press.html 4/24/2013 L.

2. 4/24/2013 L. 2. 3. 120ᵒ) When point group symmetries are combined with the possible lattice cells 17 plane groups. m.Combining symmetry operations Ten different plane point groups : 1. 90ᵒ) Square (a = b. 90ᵒ) Rhombic or hexagonal (a = b. ≠ 90°) Rectangular (a b. 6 mm Five different cell lattice types: 1. 3. 6. 3 m. 4. 2 mm. 4 mm. oblique(parallelogram) (a ≠ b. 90ᵒ) Centered rectangular or diamond (a b. 5. Viciu| AC II | Symmetry in 2D 19 . 4.

in the same sense 3. Combining rotation with translation 1. Viciu| AC II | Symmetry in 2D 20 . translation by T moves the motif from 2 to 3 Or 1. The rotations will always be to the plane (the space in 2D) 2. The new rotation will be located at a distance x = T/2 x cotg /2 along perpendicular bisector of T (T=cell edge translation) Ex: 2-fold rotation followed by translation (=180) 1 180 A 2 is the motif 4/24/2013 B x The second rotation will be on T in the middle at B T 3 Steps: 1. 2-fold rotation through B moves the motif from 1 to 3 L. An -fold rotation followed by translation to it gives another rotation of the same angle (same order). 2-fold rotation through A moves the motif from 1 to 2 2.1.

green and yellow marked are independent 2-fold axes: they relate different objects pair-wise in the pattern no any pair of the blue and one of the red. green or yellow 2-fold axis describe the same pair-wise relationship L. Viciu| AC II | Symmetry in 2D 4/24/2013 21 . red.2-fold axis combined with translation 1 Pair of motifs: T1 6 T2 8 T1 T1+T2 2 T2 4 1 4 7 9 3 2 3 •2-fold rotation at 1 combined with translation T 1 gives the rotation 6 (rotation 6 is translated to 7 by T2) •2-fold rotation at 1 combined with translation T 2 gives the rotation 8 (rotation 8 is translated to 9 by T1) •2-fold rotation at 1 combined with translation T 1+T2 gives the rotation in the middle The blue.

6-fold axis combined with translation 6-fold axis contains 2/6. Viciu| AC II | Symmetry in 2D All the operations of a 3-fold axis combined with translation and of a 2-fold axis combined with translation will be included for a p6 plane group 22 . 2/2 rotations 4/24/2013 L. 2/3.

(0 0) . 0 ½ ) Four fold axis Three non-equivalent 3-fold axes to the plane 00. ½ 0. One non-equivalent 2-fold axis to the plane. 1/3 2/3) and ( ½ 0) 4/24/2013 L. 0 ½ ) One non-equivalent 6-fold axes to the plane. One non-equivalent 3-fold axis to the plane. ½ ½) and ( ½ 0.Combination of the rotation axes with a plane lattice = translation Two fold axis Three fold axis Four non-equivalent 2-fold axes to the plane (0 0. (00. 2/3 1/3. Viciu| AC II | Symmetry in 2D Martin Buerger: An introduction to fundamental geometric features of crystals 23 . (2/3 1/3 . ½ ½ . 1/3 2/3) Six fold axis Two non-equivalent 4-fold axes to the plane.

A rectangular cell 1 1 2 1 . Combining a reflection with translation A reflection combined with a translation to it is another reflection at ½ of that perpendicular translation 1.Pair of motifs 1 2 3 2 3 Translation *2 *the mirror 2 is situated at ½ distance of the translation The mirror 2 is independent from 1 because the position of the objects (1 and 2) relative to the mirror in the center (2)of the cell is distinct from the position of the same objects relative to the first mirror (1) 4/24/2013 L.2. Viciu| AC II | Symmetry in 2D 24 .

Viciu| AC II | Symmetry in 2D 25 . A centered rectangular cell 1 and 2 are equivalent because we must have a motif in the center A glide line results in here 21 .Pair of motifs 1 22 11 1 2 2 12 A glide is the result of a reflection and a translation 1 T T *T(T+T)=glide plane The glide will be at the half distance of T T 4/24/2013 L.2.

Gliding 3’ half of Tparallel gives 3 26 . Combining a glide with a translation 1.Motif g1 2 g2 1 3’ T() 4/24/2013 3 L. Viciu| AC II | Symmetry in 2D Reflecting 1 by a mirror in the center of the edges gives 3’.3. A rectangular cell 1 gliding 2 Translatio n 3 g1 2 1 g2 gliding by g2 3 The glide g2 is situated at half of the translation which is perpendicular to it .

Viciu| AC II | Symmetry in 2D 27 .2. A centered rectangular cell Combining a glide plane with a translation in a centered rectangular lattice gives a mirror plane situated at ½ of T/2. g1 2 4/24/2013 g2 1 L.

Viciu| AC II | Symmetry in 2D 28 .4. Combining two reflections • The operation of applying two reflections in which the mirror planes (1 and 2) are making an angle with each other is the same with the rotation by an 2 angle 1 1 1’ 2 Guide to the eye 2 Two reflections: 1 1’ by reflection on 1 1’ 2 by reflection on 2 One rotation: 1 2 by two times rotation 1 2 1 1' 2 rotation by 2 4/24/2013 L.

Combining a rotation with a reflection A rotation by followed by a reflection 1 will result in another reflection which will be situated at an angle /2 relative to the first reflection 1 2 3 3 1 1 2 2 rotationby reflection by 1 1 2 3 reflection by 2 4/24/2013 L.5. Viciu| AC II | Symmetry in 2D 29 .

Viciu| AC II | Symmetry in 2D 30 .Combining symmetry operations 1. Oblique (parallelogram) (a ≠ b. ≠ 90°) p1 p2 Plane groups p1 and p2 p stands for the fact that we have only one lattice point per cell primitive lattice Examples of motifs having point group 1: (The motif itself should have no symmetry) Examples of motifs having point group 2: (The motif itself should have a 2-fold axis) 4/24/2013 and and L.

cmm2: 2-fold axis on z 3. pgm2. The addition of 1 is often used as a place holder to ensure the mirror or glide line is correctly placed ex: p3m1 and p31m 4/24/2013 L. The highest multiplicity axis or if only one symmetry axis present they are on z Ex: p4mm: 4-fold axis in the z direction. The orientation of the symmetry elements: to coordinate system x. Viciu| AC II | Symmetry in 2D my m x m z 31 . y and z. First letter: p or c translation symmetry + type of centering 2.Plane group symbol rules/meaning 1. p3m1: 3-fold axis in the z direction The highest symmetry axis is mentioned first and the rest are omitted ex: p4mmm: 4-fold axis on z and two 2-fold axes are omitted If highest multiplicity axis is 2-fold the sequence is x-y-z ex: pmm2.

pmm2 and pgg2 pmg2 Possible motifs: 4/24/2013 pmm2 pgg2 m 2mm L. 90ᵒ) Plane groups: pm.2. Rectangular (a b. Viciu| AC II | Symmetry in 2D 32 . pg. pmg2.

Examples of Rectangular plane groups with glide lines motif: motif: pmg2 pgg2 pmg2 4/24/2013 L.2. Viciu| AC II | Symmetry in 2D pgg2 33 .

p4mm and p4gm Possible motifs: 4/24/2013 4 4mm L. 90ᵒ) Plane groups: p4. Square (a = b.3. Viciu| AC II | Symmetry in 2D 34 .

then is a p4 plane group If “Yes”. Is the mirror line passing through a 4-fold axis? If “Yes” then the plane group is p4mm If “No” then the group is a p4mg 4/24/2013 L. 3. Is there a 4-fold axis? It should be otherwise it cannot be a square lattice 2.Questions to recognize a square plane group 1. Is there a mirror line in there? If No. Viciu| AC II | Symmetry in 2D 35 .

Centered rectangular (a b. 90ᵒ) The dash lined cell is known as diamond or rhombus cell Plane groups: cm and cmm2 cmm2 Possible motifs: m 4/24/2013 2mm L.4. Viciu| AC II | Symmetry in 2D 36 .

Therefore it is the standard cell 4/24/2013 L.Diamond vs. Viciu| AC II | Symmetry in 2D 37 . centered rectangular The diamond lattice has a mirror through it such that always a = b but the angle is general The centered rectangular lattice has now 2 atoms per unit cell a a=b The centered rectangular lattice has 2-fold redundancy (two diamond unit cells) but it has the big advantage of an orthogonal coordinate system.

120ᵒ) Plane groups: p3.5. Rhombic or hexagonal (a = b. p31m. p6 and p6mm Possible motifs: 4/24/2013 6 L. Viciu| AC II | Symmetry in 2D 6mm 3 3m 38 . p3m1.

**How the motifs are oriented in p3m plane
**

group

p3m1

The mirrors are to the translation

(the translation comes in the middle of the

mirrors)

p31m

The translation is along

the mirror planes

**On the second place in the plane group symbol comes what is to
**

the cell edge and on the third place comes what is to the cell edge

4/23/2013

L. Viciu| AC II | Symmetry in 2D

39

**When we have translations which are inclined to the mirrors like in
**

p3m1 plane group, a glide is always interleaved between the two

mirrors

The glide is parallel to the mirrors at half distance between them

1

**a) the inclination of translation
**

relative to the mirrors

4/23/2013

2

**b) the location of glide (between the
**

mirrors at the half distance)

L. Viciu| AC II | Symmetry in 2D

40

**When we have translations which are inclined to the mirrors like in
**

p31m plane group, a glide is always interleaved between the two

mirrors.

The glide is parallel to the mirrors at half distance between them.

**a) The inclination of the translation
**

relative to the mirrors

4/23/2013

**b) The location of the glides (between
**

the mirrors at the half distance)

L. Viciu| AC II | Symmetry in 2D

41

4/23/2013 L. p3m1 +p31m When we add the symmetry elements we should make sure that all the symmetry elements are left invariant (we don’t create additional translations or consequently more axes and planes. Viciu| AC II | Symmetry in 2D 42 .The p6mm plane group has the symmetry elements of both p3m1 and p31m groups because both of these groups are present simultaneously in p6mm plane group.

3. 4. Viciu| AC II | Symmetry in 2D 43 .Symmetry Elements of the 2D Space Groups 4/23/2013 Unit cell edge mirror line glide line 2. 6 – fold axes L.

Viciu| AC II | Symmetry in 2D 44 . y) The 2 – fold axes place the atoms at the opposite direction x It is possible to say also 1-x 1-y y But is more esthetic to give the positions x y and 4/23/2013 1-y 1-x xy L.The equivalence of atom positions results from translation y x x y x The atom will be then moved by translation to every lattice point y The atom at the lattice point has the coordinates: (x.

Has mirrors at 45°? Yes: p4mm No: p4gm 3. centre off mirrors? Yes: p31m No: p3m1 3.1. Highest order rotation? 6-fold 4-fold 3-fold 2-fold 2. Has reflection? Yes No p6mm 3. Has rot. Has perpendicular reflections? Yes No p6 Has rot. Viciu| AC II | Symmetry in 2D p4 p3 Has glide reflection? Yes: pgg2 No: p2 Has glide reflection? Yes: pg No: p1 45 . centre off mirrors? Yes: cmm2 none 4/23/2013 No: pmm2 pmg2 Has glide axis off mirrors? Yes: cm No: pm L.

molecules. 4/23/2013 L. This can be a molecule. Locate a single lattice point for each occurrence of the motif. 5. a shape or group of shapes. Identify any symmetry elements in the motif. 2. Connect the lattice points to form the unit cell. atom. Determine the plane group by comparing the symmetry elements present to the 17 plane patterns. 4. Viciu| AC II | Symmetry in 2D 46 .Fundamental Steps in Plane Groups Identification 1. group of atoms. The motif can usually be discovered by noting the periodicity of the pattern. Locate the motif present in the pattern. 3. It is a good idea to locate the lattice points at a symmetry element location.

4/23/2013 L. Viciu| AC II | Symmetry in 2D 47 .Finding the plane group No symmetry besides translation: The lattice type is oblique. plane group p1. Each unit mesh (unit cell) contains 1 white bird and 1 blue bird.

plane group p1.Finding the plane group No symmetry besides translation: The lattice type is oblique. Viciu| AC II | Symmetry in 2D 48 . 4/23/2013 L. Each unit mesh (unit cell) contains 1 white bird and 1 blue bird.

Viciu| AC II | Symmetry in 2D 49 .Finding the plane group 4/23/2013 L.

Has rotation centers off mirrors? A: yes 4. Highest order rotation? A: 2 2. Viciu| AC II | Symmetry in 2D 50 . Space group: A: cmm2 4/23/2013 L.Finding the plane group 1. Has reflections? A: yes 3.

Symmetry elements: -2-fold axis -Two mirror lines ( to each other) . Viciu| AC II | Symmetry in 2D 51 .Finding the plane group The unit cell is square.Two glide lines Plane group: cmm2 4/23/2013 L.

Finding the plane group 4/23/2013 L. Viciu| AC II | Symmetry in 2D 52 .

Highest order rotation? A: 3 2. Space group: A: p3m1 4/23/2013 L. Viciu| AC II | Symmetry in 2D 53 .Finding the plane group 1. Has reflections? A: yes 3. Has rotation centers off mirrors? A: No 4.

Viciu| AC II | Symmetry in 2D 54 .Finding the plane group 4/23/2013 L.

Space group: A: p6mm 4/23/2013 L. Has reflections? A: yes 3. Viciu| AC II | Symmetry in 2D 55 .Finding the plane group 1. Highest order rotation? A: 6 2.

Viciu| AC II | Symmetry in 2D Christopher Hammond: The basics of crystallography and diffraction (third edition) 56 .Finding the plane group 4/23/2013 L.

Finding the plane group 4/23/2013 L. Viciu| AC II | Symmetry in 2D Christopher Hammond: The basics of crystallography and diffraction (third edition) 57 .

Finding the plane group 4/23/2013 L. Viciu| AC II | Symmetry in 2D 58 .

p4gm 4/23/2013 L. Viciu| AC II | Symmetry in 2D 59 .

Finding the plane group 4/23/2013 L. Viciu| AC II | Symmetry in 2D 60 .

Finding the plane group 4/23/2013 L. Viciu| AC II | Symmetry in 2D 61 .

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