Solid State Theory Physics 545

Symmetry and Introduction to Group Theory

Symmetry is all around us and i a f d S t i ll d d is fundamental property of nature. t l t f t

Symmetry and Introduction to Group Theory y y p y

The term symmetry is derived from the Greek word symmetria which means measured together. An object is symmetric if one part (e.g. one side) of it is the same* as all of the other parts. You know intuitively if something is symmetric but we require a p g y q precise method to describe how an object or molecule is symmetric.

Group theory is a very powerful mathematical tool that allows us to rationalize and simplify many p p y y problems in Chemistry. A g p consists of y group a set of symmetry elements (and associated symmetry operations) that completely describe the symmetry of an object.

We will use some aspects of group theory to help us understand the bonding and spectroscopic features of molecules.

Space transformations. Translation symmetry.

Crystallography is largely based Group Theory (symmetry). Symmetry operations transform space into itself Simplest itself. symmetry operator is unity operator(=does nothing). (=Lattice is invariant with respect to symmetry operations) Translation operator TR, replaces radius vector of every operator, point, r, by r=r+R.

Symmetry a state in which parts on opposite sides of a plane, line, or point display arrangements that are related to one another via a symmetry operation such as translation, rotation, reflection or inversion.

Divided into two parts by a plane p y p

Mirror plane (symmetry element)

Have no symmetry remaining : Asymmetric units

Asymmetric unit A t i it
Recall that the unit cell of a crystal is the smallest 3-D geometric 3D figure that can be stacked without rotation to form the lattice. The asymmetric unit is the smallest part of a crystal structure from which the complete structure can be built using space group symmetry symmetry. The asymmetric unit may consist of only a part of a molecule, or it can contain more than one molecule, if the molecules not related by symmetry. t

Protein Crystal Contacts by Eric Martz, April 2001. Martz 2001 http://molvis.sdsc.edu/protexpl/xtlcon.htm

Group Theory
mathematical method a molecules symmetry

information about its properties

(i.e., structure spectra polarity, chirality, etc) (i e structure, spectra, polarity chirality etc )

A-B-A is different from A-A-B.

O C

However, important aspects of the symmetry of H2O and CF2Cl2 are the same.

Symmetry and Point Groups

Point groups have symmetry about a single point at the center of mass of the system. Symmetry elements are geometric entities about which a symmetry operation can be performed. In a point group, all symmetry elements must pass through the center of mass (the point). A symmetry operation is the action that produces an object identical to the initial object object. The symmetry elements and related operations that we will find in molecules are:
Element Rotation axis, Cn Improper rotation axis, Sn Plane of symmetry, Center of symmetry, i y y Operation n-fold rotation n-fold improper rotation Reflection Inversion Identity, E

The Identity operation does nothing to the object it is necessary for mathematical completeness, as we will see later.

There are two naming systems commonly used in describing symmetry elements 1. 1 The Schoenflies notation used extensively by spectroscopists 2. The Hermann-Mauguin or international notation preferred by cystallographers

Symmetry Operations/Elements
A molecule or object is said to possess a particular operation if that operation when applied leaves the molecule unchanged. Each operation is performed relative to a point, line, or plane - called a symmetry element. There are 5 kinds of operations 1. Identity 1 Id tit 2. n-Fold Rotations 3. Reflection 4. Inversion 5. Improper n-Fold Rotation

The Symmetry El Th 5 S Elements

Identity (C1 E or 1)
Rotation by 360 around any randomly chosen axes through y y y g the molecule returns it to original position. Any direction in any object is a C1 axis; rotation by 360 restores original 360 orientation. Schoenflies : C is the symbol given to a rotational axis f y g 1 indicates rotation by 360 Hermann Mauguin Hermann-Mauguin : 1 for 1-fold rotation 1 fold Operation: act of rotating molecule through 360 Element: axis of symmetry (i.e. the rotation axis). (i e axis)

Sy Symmetry Elements et y e e ts Rotation

turns all the points in the asymmetric unit around one point, the center of rotation. A rotation does not change t ti t ti d t h the handedness of figures in the plane. The center of rotation is the only invariant point (point that maps onto itself).

Good introductory symmetry websites http://mathforum.org/sum95/suzanne/symsusan.html http://www.ucs.mun.ca/~mathed/Geometry/Transformations/symmetry.html

Rotation axes (Cn or n)

Rotations through angles other than 360. Operation: act of rotation Element: rotation axis Symbol for a symmetry element for which the operation is a rotation of 360/n
C2 = 180 , C3 = 120 , C4 = 90 , C5 = 72 , C6 = 60 rotation, etc.

Schoenflies : Cn HermannMauguin : n. The molecule has an n-fold axis of symmetry. An object may possess several rotation axes and in such a case the one (or j yp ( more) with the greatest value of n is called the principal axes of rotation.

n-fold rotation - a rotation of 360/n about the Cn axis (n = 1 to )

O(1)

180
H(3)

O(1)

H(2)

H(3)

H(2)

In water there is a C2 axis so we can perform a 2-fold (180) rotation to get the identical arrangement of atoms.
H(2)

H(3)

H(4)

120
N(1)

120
N(1) N(1)

H(4)

H(3)

H(2)

H(4)

H(3)

H(2)

In ammonia there is a C3 axis so we can perform 3-fold (120) rotations to get identical arrangement of atoms.

The Principal axis in an object is the highest order rotation axis. It p j g is usually easy to identify the principle axis and this is typically assigned to the z-axis if we are using Cartesian coordinates.

Ethane, C2H6

Benzene, C6H6

The principal axis is the three-fold axis containing the C-C bond.

The principal axis is the six-fold axis through the center of the ring. g g

The principal axis in a tetrahedron is a three-fold axis going through one vertex and the center of the object.

Sy Symmetry Elements et y e e ts Reflection

flips all points in the asymmetric unit over a line which is called the mirror, line, mirror and thereby changes the handedness of any figures in the asymmetric unit. The i t l Th points along the mirror line th i li are all invariant points (points that map onto themselves) under a reflection.

Mirror planes ( or m) Mi l )
Mirror reflection through a plane. Operation: act of reflection Element: mirror plane Schoenflies notation: Horizontal mirror plane ( h) : plane perpendicular to the principal rotation axis Vertical mirror plane ( v) : plane includes principal rotation axis Diagonal mirror plane ( d) : p g p ) plane includes p principal rotation axis and bisects p the angle between a pair of 2-fold rotation axes that are normal (perpendicular) to principal rotation axis. Schoenflies : h d S h fl h, v, HermannMauguin : m

Reflection across a plane of symmetry, (mirror plane)

O(1)

v
H(3)

O(1)

H(2)

H(3)

H(2)

O(1)

v
H(3) H(2)

O(1)

H(2)

H(3)

Handedness is changed by reflection!

These mirror planes are called vertical mirror vertical planes, v, because they contain the principal axis. The reflection illustrated in the top diagram is through a mirror plane perpendicular to the plane of the water molecule. The plane shown on the bottom is in the same plane as the water molecule.

Notes about reflection operations: - A reflection operation exchanges one half of the object with the reflection of the other half. - Reflection planes may be vertical, horizontal or dihedral ( p y (more on d later). ) - Two successive reflections are equivalent to the identity operation (nothing is moved). h A horizontal mirror plane, h, is horizontal
perpendicular to the principal axis. This must be the xy-plane if the zaxis is the principal axis. p p In benzene, the h is in the plane of the molecule it reflects each atom onto itself.

Vertical and dihedral mirror planes of geometric shapes.

Sy Symmetry Elements et y e e ts Inversion every point on one side of a center of symmetry has a similar point at an equal i il i t t l distance on the opposite side of the center of symmetry.

Centres f i C t of inversion (centre of symmetry, i or 1 ) i ( t f t

Operation: inversion through this point Element: point Straight line drawn through centre of inversion from any point of the molecule will meet an equivalent point at an equal distance beyond the center. ill t i l t i t t l di t b d th t Schoenflies : i HermannMauguin : 1 Molecules possessing a center of inversion are centrosymmetric

Inversion and centers of symmetry, i (inversion centers) In this operation, every part of the object is reflected through the inversion center, which must be at the center of mass of the object.
1F
Cl 2

2F
Br 2

Cl 1

i
2 2 Br 1

Br 1

1 1 Br

1 Cl

F2

2 Cl

F1

i
[x, y, z] [-x, -y, -z]

We ill t W will not consider th matrix approach t each of th symmetry operations i thi id the ti h to h f the t ti in this course but it is particularly helpful for understanding what the inversion operation does. The inversion operation takes a point or object at [x, y, z] to [-x, -y, -z].

Axes of rotary inversion (improper rotation Sn or n ) A f t i i (i t ti S

Involves a combination or elements and operations Schoenflies : Sn Element: axis of rotatory reflection The operation is a combination of rotation by 360/n (Cn) followed by reflection in a plane normal ( h) to the Sn axis.

Hermann-Mauguin : g

Element: axis of rotatory inversion. The operation is a combination of rotation by 360 /n (n) 360/n followed by inversion through a point (1).

n-fold improper rotation, Snm (associated with an improper rotation axis or a rotation reflection axis) This operation involves a rotation of 360/n rotation-reflection 360 /n followed by a reflection perpendicular to the axis. It is a single operation and is labeled in the same manner as proper rotations.
F1 F4 F2

S41
F2 F3
F1 F2

F1
H4 F3 F4

H1 C
H3

H2

S41
H2 H1 C H4 H3

90
F3 F4

C21

S42
H3 H2 C H1 H4

Note that: S1 = , S2 = i, and sometimes S2n = Cn (e.g. in box) this makes more sense when you examine the matrices that describe the operations.

Symmetry Elements in Arrays Translational symmetry elements

Screw axis
: general symbol for a screw axis is Nn, where N is the order (2, 3, 4 or 6) of the axis ( ) (a) A twofold screw axis, 21 , (b) A fourfold screw axis, 41 :S Screw axes are very common i protein structures in t i t t Glide plane (c) p ( ) : combination of a mirror plane and a translation operation parallel to it

Sy Symmetry Elements et y e e ts
Glide reflections reflects the asymmetric unit across a mirror line and then translates parallel to the mirror. p A glide reflection changes the handedness of figures in the asymmetric unit. There are no unit invariant points (points that map onto themselves) under a glide reflection. reflection

Symmetry Elements
Screw axes rotation about the axis of symmetry by 360/n, followed by a translation parallel to the axis by r/n of the unit cell length i b / f th it ll l th in that direction.

Diagram from: http://www-structure.llnl.gov/xray/101index.html

Sy Symmetry Elements et y e e ts Translation

moves all the points in the asymmetric unit the same distance in the same direction. This has no effect on the handedness of figures in the plane. There are no invariant points (points that map onto themselves) under a translation.

A lesson in symmetry from M. C. Escher y y

To be a group several conditions must be met :

1. The group multiplication table must be closed. Consider C id H2O which has E C2 and 2 sv' hi h h E, d 's. i.e., of course etc
' C2 V V

C 2 C2 E

The group multiplication table obtained is therefore:

E E C2 v 'v E C2 v 'v C2 C2 E 'v v v v 'v E C2 'v 'v v C2 E

To be a group several conditions must be met :

2. Must have an identity ( E ).

3. All elements must have an inverse. i.e., for a given operation ( A ) there must exist an operation ( B ) such that AB = E

Point group (point symmetry)

: All molecules characterized by 32 different combinations of symmetry elements l l h t i db diff t bi ti f l

Space group ( point & translational symmetry)

: Th are 230 possible arrangements of symmetry elements in the solid state. There ibl t f t l t i th lid t t Any crystal must belong to one (and only one) space group.

There are two naming systems commonly used in describing symmetry elements g y y g y y 1. The Schoenflies notation used extensively by spectroscopists 2. The Hermann-Mauguin or international notation preferred by cystallographers Hermann Mauguin

Typical space group symbols are: P1, C2/m Ibca R3 , Fm3m P212121. C2/m, Ibca, Fm3m, P means primitive, i ii A, B , or C means centred on the face perpendicular to the a, b or c axis, F means centred on all the faces, I means body centred -- centred in the middle of the cell -R means rhombohedral,

d) three-fold axis ) Reflection a) Mirror plane Inversion n-Fold Rotations b) two-fold axis ) e) Center of symmetry

c) two-fold axis + mirror planes f) four-fold inversion axis

The symmetry classification of molecules

The groups C1, Ci and Cs C1 : no element other than the identity Ci : identity and inversion alone Cs : identity and a mirror plane alone
Cn

The groups Cn Cnv and Cnh Cn, Cn : n-fold rotation axis

= n / 2

C4

Cnv : identity, Cn axis plus n vertical mirror planes v identity Cnh : identity and an n-fold rotation principal axis plus a horizontal mirror plane h l

The groups Dn, Dnh and Dnd Dn : n-fold principal axis and n two-fold axes perpendicular to Cn

Dnh : molecule also possesses a horizontal mirror plane Dnd : in addition to the elements of Dn possesses n dihedral mirror planes d
Cn

C2 C2 C2 C2

D4

The cubic groups Td and Oh : groups of the regular tetrahedron (e.g. CH4) and regular octahedron (e.g. SF6), respectively. T or O : object possesses the rotational symmetry of the tetrahedron or the octahedron, but none of their planes of reflection Th : based on T but also contains a center of inversion

The full rotation group R3 : consists of an infinite number of rotation axes with all possible values of n n. A sphere and an atom belong to R3, but no molecule does. The groups Sn Sn : Molecules not already classified possessing one Sn axis S2 Ci

32 Point Groups

Triclinic Monoclinic Orthorhombic Tetragonal Trigonal Hexagonal H l Cubic

1* 2* 222 4* 3* 6* 23

-1

m* mm2*
-4 -3 -6 6

2/m

mmm
4/m 32 6/m 432 422 3 m* 622 -43m 4mm* -3m 6mm* -62m 62 6/mmm -42m 4/mmm

m-3

m-3m

The 11 centrosymmetric point groups are shown in red, the 11 enantiomorphic point groups are shown g , polar point groups are shown with an asterisk *. (Note that in the above table, p g p ( , in green, and the 10 p inversion axes are written with a minus sign in front of the axis symbol.)

230 space groups

1-2 3-15 16-24 25-46 47-74 75-82 83-88 89-98 99-110 111-122 111 122 123-142 143-148 149-155 149 155 156-161 162-167 168-176 168 176 177-186 187-194 195 206 195-206 206-230 : Triclinic, classes 1 and -1 : Monoclinic, classes 2, m and 2/m : Orthorhombic, class 222 : Orthorhombic, class mm2 : Orthorhombic, class mmm : Tetragonal, classes 4 and -4 : Tetragonal, class 4/m : Tetragonal, class 422 : Tetragonal, class 4mm : Tetragonal, T l class -42m l 42 : Tetragonal, class 4/mmm : Trigonal, classes 3 and -3 : Trigonal, Ti l class 32 l : Trigonal, class 3m : Trigonal, class -3m : Hexagonal Hexagonal, classes 6, -6 and 6/m 6 6 : Hexagonal, classes 622 and 6mm : Hexagonal, classes -6m2 and 6/mmm : Cubic Cubic, classes 23 and m 3 m-3 : Cubic, classes 432, -43m and m-3m

Triclinic system

Center of symmetry

Monoclinic system M li i t

Trigonal system

32 Point Groups P i G

7 Crystal Systems
cub c cubic monoclinic orthorhombic tetragonal triclinic trigonal hexagonal

Crystal System Triclinic Monoclinic Orthorhombic Tetragonal Trigonal Hexagonal Cubic

External Minimum Symmetry None One 2-fold axis, || to b (b unique) Three perpendicular 2 folds 2-folds One 4-fold axis, parallel c One 3-fold axis One 6-fold axis Four 3-folds along space diagonal

Unit Cell Properties a, b, c, al, be, ga, a, b, c, 90, be, 90 a, b, c, 90, 90, 90 a, a, c, 90, 90, 90 a, a, c, 90, 90, 120 a, a, c, 90, 90, 120 a, a, ,a, 90, 90, 90

The combination of all available symmetry operations (point groups plus glides and screws) within the seven crystal systems equals 230 combinations, combinations called the 230 Space Groups. The International Tables list those by symbol and number, together with symmetry operators, origins, ith t t i i reflection conditions, and space group projection diagrams. Inversion symmetry elements are not allowed when dealing with protein g p crystals (all amino acids present in proteins have the L stereochemical configuration; the inverse, the D configuration, cant be found in proteins.) Therefore, the number of space groups is reduced from 230 for small molecules to 65 for proteins.

Page 151, Vol. I. from International Tables for X-Ray y g p y, Crystallography, 1965 edition

Identification of the Space Group is called indexing the crystal. p p g y The International Tables for X-ray Crystallography tell us a huge amount of information about any given space group. For instance, If we look up space group P2 we fi d i h a 2 f ld rotation axis l k P2, find it has 2-fold i i and the following symmetry equivalent positions:
X -X , , Y Y , Z , -Z

and an asymmetric unit defined by: 0x 1 0y 1 0 z 1/2

An interactive tutorial on Space Groups can be found on-line in Bernhard Rupps Crystallography 101 Course: http://www structure llnl gov/Xray/tutorial/spcgrps htm http://www-structure.llnl.gov/Xray/tutorial/spcgrps.htm