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classical mechanics ...study materials for space group in classical mechanics

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85 vizualizări15 paginiclassical mechanics ...study materials for space group in classical mechanics

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From the study of angles between faces and cleavage planes of crystals T. Bergman and R. Hauy concluded, independently, around 1780, that all crystals consist of a masonry-type arrangement of equal parallelepipedal building bricks. Later it was recognized that there are seven crystallographic unit cells of crystals. The Seven Systems of Crystals are now usually grouped in terms of their axes of symmetry: 1. Cubic System with four threefold axes (along cubic diagonals) 2. Tetragonal System with one fourfold axis (through the centers of the two square faces). 3. Orthorhombic System with three twofold axes (through the centers of opposite faces). 4. Trigonal (or Rhombohedral) System with one threefold axis. 5. Hexagonal System with one sixfold axis. 6. Monoclinic System with one twofold axis. 7. Triclinic System with no axes of symmetry. The trigonal system can be considered as a subdivision of the hexagonal unit. On this basis there would be only six different crystal systems, but conventionally, the trigonal system (also called the rhombohedral system) is retained separately. Figure 2.1 shows two rhombohedral cells within a hexagonal cell. A crystal lattice is an array of points arranged according to the symmetry of the crystal system. Connecting the points produces the lattice that can be divided into identical parallelepipeds. This parallelepiped is the unit cell. The space lattice can be reproduced by repeating the unit cells in three dimensions. The seven basic primitive space lattices (P) correspond to the seven systems. There are variations of the primitive cells produced by lattice points in the center of cells (bodycentered cells, I) or in the center of faces (face-centered cells, F). Basecentered orthorhombic and monoclinic lattices are designated by C. Primitive cells contain one lattice point (8 1=8). Body-centered cells

Point Groups

Figure 2.1. Two rhombohedral cell are shown within a hexagonal cell (lighter lines).

(Source: Crystal Maker, by David Palmer, Crystal maker Software Ltd., Beg Groke Science Park, Bldg. 5, Sandy Lane, Yarnton, Oxfordshire, OX51PK, UK.)

contain two lattice points (1 8 1=8). Face-centered cells contain four lattice points (8 1=8 6 1=2). Base-centered cells contain two lattice points (8 1=8 2 1=2). It might seem that many space lattices are possible, but A. Bravais demonstrated that there are only 14 space lattices, now known as the 14 Bravais Lattices. These Seven Systems of Crystals and 14 Bravais Lattices are shown in Table 2.1 and Figure 2.2.

Symmetry is the fundamental basis for descriptions and classification of crystal structures. The use of symmetry made it possible for early investigators to derive the classification of crystals in the seven systems, 14 Bravais lattices, 32 crystal classes, and the 230 space groups before the discovery of X-ray crystallography. Here we examine symmetry elements needed for the point groups used for discrete molecules or objects. Then we examine additional operations needed for space groups used for crystal structures. The presence of an n-fold axis (Cn ) of symmetry requires that an object be invariant to rotation through 3608/n. The square planar PtCl2 (Fig4 ure 2.3) has a C4 axis through the center of and perpendicular to the plane, two equivalent C2 axes through the centers of the edges and Pt, and two equivalent C2 axes through diagonally arranged Cl atoms and Pt. There are two equivalent symmetry (mirror) planes (s) through the centers of the edges and Pt and two equivalent symmetry planes through diagonal Cl atoms and Pt. Such symmetry planes through the major (highest order) Cn axis are called vertical planes (sv ). There is another symmetry plane through Pt and all Cl atoms. Such a plane perpendicular to the major axis is called a horizontal plane (sh ). The Pt atom is located at a center of symmetry (i) because inversion of any Cl atom (or any point) through the inversion center (the origin) gives an equivalent Cl atom (or an equivalent point). There is another symmetry element or operation needed for discrete molecules, the improper rotation, Sn . A tetrahedron (the structure of

Seven systems Cubic Axes and angles abc a b g 908 Tetragonal Orthorhombic a b 6 c a b g 908 a 6 b 6 c a b g 908 14 Bravais Lattices Primitive Body centered Face centered Primitive Body centered Primitive Body centered Base face centered Face centered Trigonal or rhombohedral abc a b g 6 908 a b 6 c a b 908 g 1208 Monoclinic a 6 b 6 c a b 908 6 g or (a b 908 6 g) Triclinic a 6 b 6 c a 6 b 6 g 6 908 Primitive P Primitive Base face centered P B or C Primitive P Primitive R Lattice symbols P I F P I P I C F

Hexagonal

CH4 , Figure 2.3) has C3 axes through each apex (along one C}H bond) and C2 axes through the centers of the tetrahedral edges. There are also symmetry planes through each of these C2 axes. In addition, if we rotate about one of the C2 axes of CH4 by 908 and then reflect through a mirror plane perpendicular to the axis we have an equivalent arrangement of CH4 . This is an improper rotation, Sn , here S4 . The Sn operation involves rotation by 3608 followed by reflection through the plane /n perpendicular to the axis of rotation. All of these symmetry operations are used to assign point groups to objects or discrete molecules. Point groups are designated by Schoenflies symbols. Groups involving proper rotations only are Cn groups, T (tetrahedral), O (octahedral), or I (icosahedral) groups. Although the T, O, and I groups have no other symmetry operations, simple molecules or ions such as CH4 (Td ), SF6 (Oh ), and B12 H2 (Ih ) have many other symmetry elements. The Sn 12 groups involve only proper and improper rotations, although S2 is equivalent to i. Dihedral groups (Dn , Dnh , Dnd ) have n C2 axes perpendicular to the major Cn axis. The trigonal BF3 molecule (Figure 2.3) has C3 as the major axis and three C2 axes perpendicular to C3 . These are the symmetry operations for the D3 point group, but there is a symmetry plane perpendicular to C3 (sh , through all atoms) so the point group is D3h . The point group for PtCl2 is D4h . Ferrocene, Fe(C5 H5 )2 (Figure 2.3), 4

Point Groups

Figure 2.2. The seven Crystal Systems and the 14 Bravais Lattices.

has two dicyclopentadienyl rings: one planar ring below, and one above the Fe atom. The C5 H5 rings are in parallel planes and are staggered when viewed along the C5 axis. There are five C2 axes perpendicular to the C5 axis. There are five vertical mirror planes, each bisecting the angle between C2 axes. These are called dihedral planes, a special case of vertical planes, and the point group for Fe(C5 H5 )2 is D5d . Chemists use the Schoenflies Notation and rotation-reflection for improper rotation in assigning point groups. Crystallographers

Figure 2.3. Molecular structures of CH4 , [PtCl4 ]2 , BF3 , and ferrocene [Fe(C5 H5 )2 ].

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use the International (Hermann-Maguin) Notation and rotationinversion as improper rotation in assigning space groups. Proper rotations C1 , C2 , C3 , C4 , and C6 are designated by the numbers 1, 2, 3, 4, and 6 in the International System. Improper rotations (rotationinversion) are indicated by a bar over the number, , , , , and 1 2 3 4 6 Rotation-reflections are indicated by ~, ~, ~, ~, and ~. The result of 1 2 3 4 6 these operations on a point in a plane is shown in Figure 2.4. The results of proper rotations are shown by an unsymmetrical symbol 7. The results of both types of improper rotations are shown acting on a marker appearing as X on top and O on the bottom so that reflection in m or inversion turns it over. The rotation-inversion and rotation-reflection axes are equivalent in pairs, as shown in Table 2.2. Conventionally, these improper axes are designated as , m, , , and where 1 3 4 6 a mirror plane is indicated by m. If a mirror plane contains a proper rotation axis it is designated 2m, 3m . . . If the mirror plane is perpendicular to the axis, it is 2/m, 3/m . . . Only the minimum number of symmetry elements is used, omitting other equivalent elements. The D2 group is 222, but D2h is mmm because 2/m 2/m 2/m is redundant, as the perpendicular planes require C2 axes. The group C4v is 4mm, rather than 4m, because there are two distinguishable mirror planes. The point groups I and Ih are not encountered in crystallographic groups. The symmetry elements, proper rotation, improper rotation, inversion, and reflection are required for assigning a crystal to one of the 32 crystal systems or crystallographic point groups. Two more symmetry elements involving translation are needed for crystal structuresthe screw axis, and the glide plane. The screw axis involves a combination of a proper rotation and a confined translation along the axis of rotation. The glide plane involves a combination of a proper reflection and a confined translation within the mirror plane. For a unit cell

Miller Indices

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Rotation-inversion axes 1 2 3 4 6 Equivalent rotation-reflection ~ 2 ~ 1 ~ 6 ~ 4 ~ 3 Conventional designation 1 m 3 4 6

requiring a screw axis or a glide plane for its symmetry description, the corresponding crystallographic point group is obtained by setting translation equal to zero.

Early investigators were interested in designating the faces of crystals. We choose an arbitrary lattice point as the origin and give the intercepts of the plane with the three crystallographic axes in units of a, b, and c. These three intercepts are known as the Weiss index of the plane. The numbers in the Weiss index can be positive or negative, 1 for a plane cutting at 1a, 1 for a plane cutting at 1 a (or another fraction, 2 2 etc.), or infinity for a plane parallel to an axis. The more convenient system is to use the Miller index, the reciprocal of the Weiss index. This eliminates fractions and infinity because the Miller index for a plane parallel to an axis is zero. The general Miller index is hkl for a face or a set of planes, where h is the number of equal divisions of a in the unit cell, k the divisions of b, and l the divisions of c. In Figure 2.5, two planes corresponding to two faces of an octahedron are shown, one cutting a, b, and c at 1, giving a 111 plane. The lower face or plane sharing the ab line has intercepts at 1a, 1b, and 1c, giving the Miller index 1 1 (negative values are given as the number with a bar over it). 1 Other planes are shown in Figure 2.6.

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Most crystals are imperfect, and the full symmetry is not apparent. Projection techniques are used to find the true symmetry of a crystal and its classification among the 32 crystallographic point groups. We choose the center of the crystal as the origin and construct a sphere centered at the origin. A radius is drawn from the origin normal to each face and marked as a dot on the sphere. The symmetry of all of these points belongs to one of the crystallographic point groups. The spherical projection is reduced to a more convenient planar stereographic projection. The sphere is divided into hemispheres above and below the horizontal plane. The points of the northern hemisphere are connected by rays to the south pole. The intersection of each of these rays with the horizontal plane is marked by a solid dot. The intersection with the horizontal plane with each ray from a point in the southern hemisphere to the north pole is marked by an open circle. The highest symmetry axis is chosen as vertical. The great circle is a thick line if there is a symmetry plane in this plane; otherwise, it is represented by a thinner line. Vertical symmetry planes are represented as lines (diameters) through the center. In the cubic groups there are symmetry planes tilted relative to sv and sh planes. These are shown as portions of ellipses, projections on the great circles representing the tilted planes. Twofold axes in the equatorial plane are shown as a line connecting the symbols for C2 . Special positions are those falling on the symmetry elements of the crystal or cell. Stereograms indicate these positions by the following symbols:

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2 m

The symbol for each axis appears in the great circle where its points of intersection with the sphere would project on the horizontal plane. These positions are at the center or on the great circle except for threefold and twofold axes of the cubic groups. The stereographic projections for a crystallographic point group are shown as two circles: one showing the symmetry elements, and one showing the array of points on the sphere resulting from the symmetry operations of the group acting on an initial general point. The projections of these points are solid dots for points on the upper hemisphere and are open circles for points on the lower hemisphere. A solid dot in an open circle indicates two points on the same vertical line. The two circles for stereographic projections can be combined unless the result is too cluttered for clarity.

A crystal is a well-tailored network or lattice of atoms. The construction of the lattice is directed stringently by the symmetry elements of the crystal. We can choose a central point and consider the periodical stacking around this point. Combinations of symmetry elements limit the arrangements to only 32 patternsthe 32 point groups or the 32 classes of crystals. The five proper rotations 1, 2, 3, 4, and 6 give the corresponding point groups (C1 , C2 , C3 , C4 , and C6 ) represented by the stereograms for the rotational Cn groups in Figure 2.7. The rotation-inversion axes shown in Table 2.2 produce the five point groups (Ci ), (m Cs ), (S6 ), (S4 ), 1 2 3 4 and (C3h S3 ), where Cs S1 and Ci S2 shown in Figure 2.7. Com6 binations of proper rotation axes produce six more rotational point groups (D2 , T, D4 , D3 , D6 , and O), as diagrammed in Figure 2.8. These are dihedral groups (Dn ) plus the rotational groups T and O. Combinations of proper axes perpendicular to a mirror plane produce five point groups, 1=m m , 2=m, 3=m , 4=m, and 6/m. Two of 2 6 these are identical with and shown in Figure 2.7, leaving three 2 6 additional point groups, 2=m (C2h ), 4=m (C4h ), and 6=m (C6h ) represented in Figure 2.8. Combination of a proper rotation with a vertical mirror plane (m or sv ) produces the Cnv groups, (1m m), 2mm ( mm), 3m, 4mm, and 6mm. The point group m (Cs ) is included in Figure 2.7, leaving four

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Figure 2.7. Stereograms for the six Cn point groups produced by proper rotations and those for the point groups produced by improper rotations.

Cnv groups in Figure 2.8. Combination of a proper rotation with a horizontal mirror plane (m or sh ) and a vertical plane produces six more point groups: 2/m 2/m 2/m ( mmm) (D2h ), 3/m m2 ( m2) 6 (D3h ), 4/m 2/m 2/m ( 4/m mm) (D4h ), 6/m 2/m 2/m ( 6/m mm) (D6h ), 2/m ( m ) (Th ), and 4=m2=m ( mm) (Oh ). These are shown 3 3 3 3 in Figure 2.9. These proper rotations and improper rotations and combinations of proper rotations and mirror planes produce 29 point groups. The remaining three point groups are obtained by combinations of improper axes and with proper rotations. The products are 3 4 point groups 2m (D2d ), m (D3d ), and 3m (Td ) as shown in Figure 4 3 4 2.9. These complete the 32 crystallographic point groups or crystal classes. These are grouped by Crystal Systems in Table 2.3.

The 32 crystallographic point groups result from combinations of symmetry based on a fixed point. These symmetry elements can be combined with the two translational symmetry elements: the screw

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Figure 2.8. Stereograms for the six Dn , T, and O point groups from combinations of proper rotations. Those for the three Cnh point groups from combinations of proper rotations and a horizontal mirror 6 plane [in addition to (m or C1h ) and (C3h ) shown in Figure 2.7]. Those for the Cnv point groups from 2 combinations of proper rotations and a vertical mirror plane.

axis, and the glide plane. The results of these combinations give the rest of the 230 crystallographic space groups. Thirty-two of the space groups are the same as the point groups. In the crystals belonging to the 32 point groups each unit is reproduced without alteration. In the other space groups each unit repeats with translation and rotation or reflection. Three investigators from different countries independently arrived at the 230 space groups around 1890: E. S. Federov (18531919, Russian) A. M. Schoenflies (18531928, German) W. Barlow (18451934, English) This is an impressive example of a major advancement occurring in three places at the right time. These men had to have thorough knowledge of the crystallography of the time, mathematics, and great insight.

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Figure 2.9. Stereograms for point groups from proper rotations and a plane. Stereograms for the point groups from combinations of of improper rotations and with proper rotations. 4 3 4

Table 2.4 shows the crystal systems, point groups, and the corresponding space groups. The numbers for space groups are those as derived and numbered by Schoenflies. The space groups isomorphous to each point group are indicated by a superscript (e.g., Number 194, D6h 4 ).

Designations for individual space groups use the notation proposed by Hermann and Mauguin in 1935. This notation has been adopted by the International Union of Crystallography and is in general use. The symbols provide more information than just the symmetry elements for a crystal. The first symbol is a capital letter: P for a simple or primitive lattice, I for a body-centered lattices, and F for face-centered lattices with all faces centered. Lattices with one face centered are designated A (100 planes), B (010 planes), or C (001 planes). R is the symbol for a face-centered trigonal lattice for which a primitive rhombohedral unit cell is chosen. After the general description of the unit cell a number identifies the major axis of rotation. For example,

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TABLE 2.3. The seven crystal systems and the 32 crystal classes.

Crystal system Triclinic Schoenflies symbol C1 Ci Monoclinic Cs C2 C2h Orthorhombic C2v D2 D2h Tetragonal C4 S4 C4h C4v D2d D4 D4h International symbol 1 1 m 2 2/m 2mm 222 mmm 4 4 4/m 4mm 42m 422 4/m mm Cubic Hexagonal Crystal system Rhombohedral Schoenflies symbol C3 S6 C3v D3 D3d C3h C6 C6h D3h C6v D6 D6h T Th Td O Oh International symbol 3 3 3m 32 m 3 6 6 6/m m2 6 6mm 622 6/m mm 23 m 3 43m 432 m3m

P2/m is a primitive cell with a twofold axis and a mirror plane perpendicular to the axis. Major axes are indicated by positive numbers for Cn and barred numbers, , , etc., for improper axes of rotation. Screw axes are indi2 3 cated by subscripts such as 21 , 32 , etc. A 41 screw axis involves translation of 1/4 upward for an anticlockwise rotation, 42 involves translation by 1/2 (2/4), an 43 involves translation by 3/4. Mirror planes (m) and glide planes are indicated by letters, using the letters corresponding to translation by the fractions along a particular direction as follows Translation a 2 b 2 c 2 ab bc ca , or 2 2 2 ab bc ca , or 4 4 4 Examples are given in Table 2.4. Symbol a b c n d

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TABLE 2.4. Space groups, crystal systems, point groups, and the Hermann-Mauguin Symbols.

Space group number 1 2 35 69 1015 1624 2546 4774 7580 8182 8388 8998 99110 111122 123142 143146 147148 149155 156161 162167 168173 174 175176 177182 183186 187190 191194 195199 200206 207214 215220 221230

*

Point group Crystal system Triclinic International symbol 1 1 2 Monoclinic m 2/m 222 Orthorhombic mm2 mmm 4 4 4/m Tetragonal 422 4mm 2m 4 4/m mm 3 3 Trigonal 312 3m 3m 6 6 6/m Hexagonal 622 6mm 6m2 6/m mm 23 m 3 Cubic 432 3m 4 mm 3 Schoenflies symbol C1 1 Ci 1 C2 1 (No. 3) Cs (No. 6) C2h 1 (No. 10) D2 1 (No. 16) C2v 1 D2h 28 (No. 74) C4 1 (No. 75) S4

1 1

HermannMauguin symbol P1 P1 P2 Pm P2/m P222 Pmm2 Imma P4 P 4 P4/m P422 P4mm P2m 4 P4/m mm P3 P 3 P312 P3m1 Rc 3 P6 P 6 P6/m P622 P6mm P6m2 P63 =m mc P23 Pm 3 P432 P3m 4 Pm3m

C4h 1 D4

1

C4v 1 D2d

1

1

D3 1 C3v

1

1

D3h 1 D6h (No. 194) T (No. 195) Th (No. 200) O1 (No. 207) Td (No. 215) Oh 1 (No. 221)

1 1 1 4

These are commonly used abbreviations, the full H-M symbol for Th is 2/m3 (also sometimes abbreviated as m3), 3 and the full H-M symbol for Oh is 4/m 2/m (also sometimes abbreviated as m3m. Th and Oh have centers of symmetry thus 3 I is equivalent to . 3

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Commonly, many compounds with the same formula type have the same type of structure. Usually the most common compound is chosen as representative, but it could be the first structure of the type studied. For example, hundreds of binary compounds of the MX type have the same crystal structure as NaCl. Other compounds can be described as having the NaCl (or halite, the name of the mineral) structure. If the structure being considered has slight differences, these differences can be described in terms of the reference structure. One often sees statements such as a compound has a disordered spinel (MgAl2 O4 ) type structure or an inverse spinel structure. This requires knowledge of the spinel structure because inverse or disordered terms describe variations of occupancies of octahedral and tetrahedral sites.

Many systems of notation and classification have been proposed. The well-known books by R. W. G. Wyckoff, A. F. Wells, F. C. Phillips, L. Bragg, M. J. Buerger, L. V. Azakoff, D. M Adams, and W. B. Pearson (Appendix A, Further Reading) have discussed these proposals. These proposals include close packing of atoms, nets, or prism connections, stacking of coordination polyhedra and even a crystal-algebra method. Application of most of these proposals requires familiarity with the features of many structures. Only specialists can be expected to have

Crystal system Triclinic, a Monoclinic, m Orthorhombic, o Lattice symbol P P C P C F I Tetragonal, t Hexagonal, h and Trigonal, h Rhombohedral, h Cubic, c R P F I

* x Number of atoms in the unit cell.

Structure symbol* aPx mPx mCx oPx oCx oFx oIx tPx tIx hPx hRx cPx cFx cIx

P I P

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all of the necessary information at their fingertips. None of these has general approval or wide use. Professor Pearson (see Appendix A) adopted simple notation providing useful information. His Structure Symbol gives the crystal system by a lower case letter (e.g., m for monoclinic), the lattice type by a capital letter (e.g., P for primitive), and the number of atoms in the unit cell. The structure symbols are given in Table 2.5. For example, the fluorite (CaF2 ) structure is described as cF12 for a face-centered cubic unit cell containing 12 atoms (8F and (1=8 8) (6 1=2) 4Ca2 ). The symbol for Al7 Cu2 Fe alloy is tP40, primitive tetragonal unit cell containing 40 atoms or 4Al7 Cu2 Fe units.